Polymers functionalized with nitrile compounds containing a protected amino group

ABSTRACT

A method for preparing a functionalized polymer, the method comprising the steps of (i) polymerizing monomer with a coordination catalyst to form a reactive polymer; and (ii) reacting the reactive polymer with a nitrile compound containing a protected amino group.

This application claims the benefit of International Application SerialNo. PCT/US2010/021767, filed on Jan. 22, 2010, and U.S. ProvisionalApplication Ser. No. 61/146,871, filed Jan. 23, 2009, which isincorporated herein by reference.

FIELD OF THE INVENTION

One or more embodiments of the present invention relate tofunctionalized polymers and methods for their manufacture.

BACKGROUND OF THE INVENTION

In the art of manufacturing tires, it is desirable to employ rubbervulcanizates that demonstrate reduced hysteresis, i.e., less loss ofmechanical energy to heat. For example, rubber vulcanizates that showreduced hysteresis are advantageously employed in tire components, suchas sidewalls and treads, to yield tires having desirably low rollingresistance. The hysteresis of a rubber vulcanizate is often attributedto the free polymer chain ends within the crosslinked rubber network, aswell as the dissociation of filler agglomerates.

Functionalized polymers have been employed to reduce the hysteresis ofrubber vulcanizates. The functional group of the functionalized polymermay reduce the number of free polymer chain ends via interaction withfiller particles. Also, the functional group may reduce filleragglomeration. Nevertheless, whether a particular functional groupimparted to a polymer can reduce hysteresis is often unpredictable.

Functionalized polymers may be prepared by post-polymerization treatmentof reactive polymers with certain functionalizing agents. However,whether a reactive polymer can be functionalized by treatment with aparticular functionalizing agent can be unpredictable. For example,functionalizing agents that work for one type of polymer do notnecessarily work for another type of polymer, and vice versa.

Lanthanide-based catalyst systems are known to be useful forpolymerizing conjugated diene monomers to form polydienes having a highcontent of cis-1,4 linkage. The resulting cis-1,4-polydienes may displaypseudo-living characteristics in that, upon completion of thepolymerization, some of the polymer chains possess reactive ends thatcan react with certain functionalizing agents to yield functionalizedcis-1,4-polydienes.

The cis-1,4-polydienes produced with lanthanide-based catalyst systemstypically have a linear backbone, which is believed to provide bettertensile properties, higher abrasion resistance, lower hysteresis, andbetter fatigue resistance as compared to the cis-1,4-polydienes preparedwith other catalyst systems such as titanium-, cobalt-, and nickel-basedcatalyst systems. Therefore, the cis-1,4-polydienes made withlanthanide-based catalysts are particularly suitable for use in tirecomponents such as sidewalls and treads. However, one disadvantage ofthe cis-1,4-polydienes prepared with lanthanide-based catalysts is thatthe polymers exhibit high cold flow due to their linear backbonestructure. The high cold flow causes problems during storage andtransport of the polymers and also hinders the use of automatic feedingequipment in rubber compound mixing facilities.

Because functionalized polymers are advantageous, especially in themanufacture of tires, there exists a need to develop new functionalizedpolymers that give reduced hysteresis and reduced cold flow.

SUMMARY OF THE INVENTION

One or more embodiments of the present invention provide a method forpreparing a functionalized polymer, the method comprising the steps ofpolymerizing monomer with a coordination catalyst to form a reactivepolymer and reacting the reactive polymer with a nitrile compoundcontaining a protected amino group.

Other embodiments of the present invention provide a functionalizedpolymer defined by the formula:

where π is a cis-1,4-polydiene chain having a cis-1,4-linkage contentthat is greater than 60%, R¹ is a divalent organic group, and R² and R³are each independently a monovalent organic group or a hydrolyzablegroup, or R² and R³ join to form a divalent organic group.

Other embodiments of the present invention provide a functionalizedpolymer defined by the formula:

where π is a cis-1,4-polydiene chain having a cis-1,4-linkage contentthat is greater than 60%, R¹ is a divalent organic group, and R² and R³are each independently a monovalent organic or a hydrogen atom, or R²and R³ join to form a divalent organic group.

Other embodiments of the present invention provide a functionalizedpolymer prepared by the steps of polymerizing conjugated diene monomerwith a coordination catalyst to form a reactive cis-1,4-polydiene havinga cis-1,4-linkage content that is greater than 60% and reacting thereactive cis-1,4-polydiene with a nitrile compound containing aprotected amino group.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graphical plot of cold-flow gauge (mm at 8 min) versusMooney viscosity (ML 1+4 at 100° C.) for functionalizedcis-1,4-polybutadiene prepared according to one or more embodiments ofthe present invention as compared to unfunctionalizedcis-1,4-polybutadiene.

FIG. 2 is a graphical plot of hysteresis loss (tan δ) versus Mooneyviscosity (ML 1+4 at 130° C.) for vulcanizates prepared fromfunctionalized cis-1,4-polybutadiene prepared according to one or moreembodiments of the present invention as compared to vulcanizatesprepared from unfunctionalized cis-1,4-polybutadiene.

DETAILED DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS

According to one or more embodiments of the present invention, areactive polymer is prepared by polymerizing conjugated diene monomerwith a coordination catalyst, and this reactive polymer can then befunctionalized by reaction with a nitrile compound containing aprotected amino group. The resultant functionalized polymers can be usedin the manufacture of tire components. In one or more embodiments, theresultant functionalized polymers, which include cis-1,4-polydienes,exhibit advantageous cold-flow resistance and provide tire componentsthat exhibit advantageously low hysteresis.

Examples of conjugated diene monomer include 1,3-butadiene, isoprene,1,3-pentadiene, 1,3-hexadiene, 2,3-dimethyl-1,3-butadiene,2-ethyl-1,3-butadiene, 2-methyl-1,3-pentadiene, 3-methyl-1,3-pentadiene,4-methyl-1,3-pentadiene, and 2,4-hexadiene. Mixtures of two or moreconjugated dienes may also be utilized in copolymerization.

In one or more embodiments, the reactive polymer is prepared bycoordination polymerization, wherein monomer is polymerized by using acoordination catalyst system. The key mechanistic features ofcoordination polymerization have been discussed in books (e.g., Kuran,W., Principles of Coordination Polymerization; John Wiley & Sons: NewYork, 2001) and review articles (e.g., Mulhaupt, R., MacromolecularChemistry and Physics 2003, volume 204, pages 289-327). Coordinationcatalysts are believed to initiate the polymerization of monomer by amechanism that involves the coordination or complexation of monomer toan active metal center prior to the insertion of monomer into a growingpolymer chain. An advantageous feature of coordination catalysts istheir ability to provide stereochemical control of polymerizations andthereby produce stereoregular polymers. As is known in the art, thereare numerous methods for creating coordination catalysts, but allmethods eventually generate an active intermediate that is capable ofcoordinating with monomer and inserting monomer into a covalent bondbetween an active metal center and a growing polymer chain. Thecoordination polymerization of conjugated dienes is believed to proceedvia π-allyl complexes as intermediates. Coordination catalysts can beone-, two-, three- or multi-component systems. In one or moreembodiments, a coordination catalyst may be formed by combining a heavymetal compound (e.g., a transition metal compound or alanthanide-containing compound), an alkylating agent (e.g., anorganoaluminum compound), and optionally other co-catalyst components(e.g., a Lewis acid or a Lewis base). In one or more embodiments, theheavy metal compound may be referred to as a coordinating metalcompound.

Various procedures can be used to prepare coordination catalysts. In oneor more embodiments, a coordination catalyst may be formed in situ byseparately adding the catalyst components to the monomer to bepolymerized in either a stepwise or simultaneous manner. In otherembodiments, a coordination catalyst may be preformed. That is, thecatalyst components are pre-mixed outside the polymerization systemeither in the absence of any monomer or in the presence of a smallamount of monomer. The resulting preformed catalyst composition may beaged, if desired, and then added to the monomer that is to bepolymerized.

Useful coordination catalyst systems include lanthanide-based catalystsystems. These catalyst systems may advantageously producecis-1,4-polydienes that, prior to quenching, have reactive chain endsand may be referred to as pseudo-living polymers. While othercoordination catalyst systems may also be employed, lanthanide-basedcatalysts have been found to be particularly advantageous, andtherefore, without limiting the scope of the present invention, will bediscussed in greater detail.

Practice of the present invention is not necessarily limited by theselection of any particular lanthanide-based catalyst system. In one ormore embodiments, the catalyst systems employed include (a) alanthanide-containing compound, (b) an alkylating agent, and (c) ahalogen source. In other embodiments, a compound containing anon-coordinating anion or a non-coordinating anion precursor can beemployed in lieu of a halogen source. In these or other embodiments,other organometallic compounds, Lewis bases, and/or catalyst modifierscan be employed in addition to the ingredients or components set forthabove. For example, in one embodiment, a nickel-containing compound canbe employed as a molecular weight regulator as disclosed in U.S. Pat.No. 6,699,813, which is incorporated herein by reference.

As mentioned above, the catalyst systems employed in the presentinvention can include a lanthanide-containing compound.Lanthanide-containing compounds useful in the present invention arethose compounds that include at least one atom of lanthanum, neodymium,cerium, praseodymium, promethium, samarium, europium, gadolinium,terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, anddidymium. In one embodiment, these compounds can include neodymium,lanthanum, samarium, or didymium. As used herein, the term “didymium”shall denote a commercial mixture of rare-earth elements obtained frommonazite sand. In addition, the lanthanide-containing compounds usefulin the present invention can be in the form of elemental lanthanide.

The lanthanide atom in the lanthanide-containing compounds can be invarious oxidation states including, but not limited to, the 0, +2, +3,and +4 oxidation states. In one embodiment, a trivalentlanthanide-containing compound, where the lanthanide atom is in the +3oxidation state, can be employed. Suitable lanthanide-containingcompounds include, but are not limited to, lanthanide carboxylates,lanthanide organophosphates, lanthanide organophosphonates, lanthanideorganophosphinates, lanthanide carbamates, lanthanide dithiocarbamates,lanthanide xanthates, lanthanide β-diketonates, lanthanide alkoxides oraryloxides, lanthanide halides, lanthanide pseudo-halides, lanthanideoxyhalides, and organolanthanide compounds.

In one or more embodiments, the lanthanide-containing compounds can besoluble in hydrocarbon solvents such as aromatic hydrocarbons, aliphatichydrocarbons, or cycloaliphatic hydrocarbons. Hydrocarbon-insolublelanthanide-containing compounds, however, may also be useful in thepresent invention, as they can be suspended in the polymerization mediumto form the catalytically active species.

For ease of illustration, further discussion of usefullanthanide-containing compounds will focus on neodymium compounds,although those skilled in the art will be able to select similarcompounds that are based upon other lanthanide metals.

Suitable neodymium carboxylates include, but are not limited to,neodymium formate, neodymium acetate, neodymium acrylate, neodymiummethacrylate, neodymium valerate, neodymium gluconate, neodymiumcitrate, neodymium fumarate, neodymium lactate, neodymium maleate,neodymium oxalate, neodymium 2-ethylhexanoate, neodymium neodecanoate(a.k.a., neodymium versatate), neodymium naphthenate, neodymiumstearate, neodymium oleate, neodymium benzoate, and neodymiumpicolinate.

Suitable neodymium organophosphates include, but are not limited to,neodymium dibutyl phosphate, neodymium dipentyl phosphate, neodymiumdihexyl phosphate, neodymium diheptyl phosphate, neodymium dioctylphosphate, neodymium bis(1-methylheptyl)phosphate, neodymiumbis(2-ethylhexyl)phosphate, neodymium didecyl phosphate, neodymiumdidodecyl phosphate, neodymium dioctadecyl phosphate, neodymium dioleylphosphate, neodymium diphenyl phosphate, neodymiumbis(p-nonylphenyl)phosphate, neodymium butyl(2-ethylhexyl)phosphate,neodymium (1-methylheptyl) (2-ethylhexyl)phosphate, and neodymium(2-ethylhexyl)(p-nonylphenyl)phosphate.

Suitable neodymium organophosphonates include, but are not limited to,neodymium butyl phosphonate, neodymium pentyl phosphonate, neodymiumhexyl phosphonate, neodymium heptyl phosphonate, neodymium octylphosphonate, neodymium (1-methylheptyl)phosphonate, neodymium(2-ethylhexyl)phosphonate, neodymium decyl phosphonate, neodymiumdodecyl phosphonate, neodymium octadecyl phosphonate, neodymium oleylphosphonate, neodymium phenyl phosphonate, neodymium(p-nonylphenyl)phosphonate, neodymium butyl butylphosphonate, neodymiumpentyl pentylphosphonate, neodymium hexyl hexylphosphonate, neodymiumheptyl heptylphosphonate, neodymium octyl octylphosphonate, neodymium(1-methylheptyl) (1-methylheptyl)phosphonate, neodymium (2-ethylhexyl)(2-ethylhexyl)phosphonate, neodymium decyl decylphosphonate, neodymiumdodecyl dodecylphosphonate, neodymium octadecyl octadecylphosphonate,neodymium oleyl oleylphosphonate, neodymium phenyl phenylphosphonate,neodymium (p-nonylphenyl) (p-nonylphenyl)phosphonate, neodymium butyl(2-ethylhexyl)phosphonate, neodymium (2-ethylhexyl)butylphosphonate,neodymium (1-methylheptyl) (2-ethylhexyl)phosphonate, neodymium(2-ethylhexyl) (1-methylheptyl)phosphonate, neodymium (2-ethylhexyl)(p-nonylphenyl)phosphonate, and neodymium (p-nonylphenyl)(2-ethylhexyl)phosphonate.

Suitable neodymium organophosphinates include, but are not limited to,neodymium butylphosphinate, neodymium pentylphosphinate, neodymiumhexylphosphinate, neodymium heptylphosphinate, neodymiumoctylphosphinate, neodymium (1-methylheptyl)phosphinate, neodymium(2-ethylhexyl)phosphinate, neodymium decylphosphinate, neodymiumdodecylphosphinate, neodymium octadecylphosphinate, neodymiumoleylphosphinate, neodymium phenylphosphinate, neodymium(p-nonylphenyl)phosphinate, neodymium dibutylphosphinate, neodymiumdipentylphosphinate, neodymium dihexylphosphinate, neodymiumdiheptylphosphinate, neodymium dioctylphosphinate, neodymiumbis(1-methylheptyl)phosphinate, neodymium bis(2-ethylhexyl)phosphinate,neodymium didecylphosphinate, neodymium didodecylphosphinate, neodymiumdioctadecylphosphinate, neodymium dioleylphosphinate, neodymiumdiphenylphosphinate, neodymium bis(p-nonylphenyl)phosphinate, neodymiumbutyl (2-ethylhexyl)phosphinate, neodymium(1-methylheptyl)(2-ethylhexyl)phosphinate, and neodymium(2-ethylhexyl)(p-nonylphenyl)phosphinate.

Suitable neodymium carbamates include, but are not limited to, neodymiumdimethylcarbamate, neodymium diethylcarbamate, neodymiumdiisopropylcarbamate, neodymium dibutylcarbamate, and neodymiumdibenzylcarbamate.

Suitable neodymium dithiocarbamates include, but are not limited to,neodymium dimethyldithiocarbamate, neodymium diethyldithiocarbamate,neodymium diisopropyldithiocarbamate, neodymium dibutyldithiocarbamate,and neodymium dibenzyldithiocarbamate.

Suitable neodymium xanthates include, but are not limited to, neodymiummethylxanthate, neodymium ethylxanthate, neodymium isopropylxanthate,neodymium butylxanthate, and neodymium benzylxanthate.

Suitable neodymium β-diketonates include, but are not limited to,neodymium acetylacetonate, neodymium trifluoroacetylacetonate, neodymiumhexafluoroacetylacetonate, neodymium benzoylacetonate, and neodymium2,2,6,6-tetramethyl-3,5-heptanedionate.

Suitable neodymium alkoxides or aryloxides include, but are not limitedto, neodymium methoxide, neodymium ethoxide, neodymium isopropoxide,neodymium 2-ethylhexoxide, neodymium phenoxide, neodymiumnonylphenoxide, and neodymium naphthoxide.

Suitable neodymium halides include, but are not limited to, neodymiumfluoride, neodymium chloride, neodymium bromide, and neodymium iodide.Suitable neodymium pseudo-halides include, but are not limited to,neodymium cyanide, neodymium cyanate, neodymium thiocyanate, neodymiumazide, and neodymium ferrocyanide. Suitable neodymium oxyhalidesinclude, but are not limited to, neodymium oxyfluoride, neodymiumoxychloride, and neodymium oxybromide. A Lewis base, such astetrahydrofuran (“THF”), may be employed as an aid for solubilizing thisclass of neodymium compounds in inert organic solvents. Where lanthanidehalides, lanthanide oxyhalides, or other lanthanide-containing compoundscontaining a halogen atom are employed, the lanthanide-containingcompound may also serve as all or part of the halogen source in theabove-mentioned catalyst system.

As used herein, the term organolanthanide compound refers to anylanthanide-containing compound containing at least one lanthanide-carbonbond. These compounds are predominantly, though not exclusively, thosecontaining cyclopentadienyl (“Cp”), substituted cyclopentadienyl, allyl,and substituted allyl ligands. Suitable organolanthanide compoundsinclude, but are not limited to, Cp₃Ln, Cp₂LnR, Cp₂LnCl, CpLnCl₂,CpLn(cyclooctatetraene), (C₅Me₅)₂LnR, LnR₃, Ln(allyl)₃, andLn(allyl)₂Cl, where Ln represents a lanthanide atom, and R represents ahydrocarbyl group. In one or more embodiments, hydrocarbyl groups usefulin the present invention may contain heteroatoms such as, for example,nitrogen, oxygen, boron, silicon, sulfur, and phosphorus atoms.

As mentioned above, the catalyst systems employed in the presentinvention can include an alkylating agent. In one or more embodiments,alkylating agents, which may also be referred to as hydrocarbylatingagents, include organometallic compounds that can transfer one or morehydrocarbyl groups to another metal. Typically, these agents includeorganometallic compounds of electropositive metals such as Groups 1, 2,and 3 metals (Groups IA, IIA, and IIIA metals). Alkylating agents usefulin the present invention include, but are not limited to, organoaluminumand organomagnesium compounds. As used herein, the term organoaluminumcompound refers to any aluminum compound containing at least onealuminum-carbon bond. In one or more embodiments, organoaluminumcompounds that are soluble in a hydrocarbon solvent can be employed. Asused herein, the term organomagnesium compound refers to any magnesiumcompound that contains at least one magnesium-carbon bond. In one ormore embodiments, organomagnesium compounds that are soluble in ahydrocarbon can be employed. As will be described in more detail below,several species of suitable alkylating agents can be in the form of ahalide. Where the alkylating agent includes a halogen atom, thealkylating agent may also serve as all or part of the halogen source inthe above-mentioned catalyst system.

In one or more embodiments, organoaluminum compounds that can beutilized include those represented by the general formulaAlR_(n)X_(3-n), where each R independently can be a monovalent organicgroup that is attached to the aluminum atom via a carbon atom, whereeach X independently can be a hydrogen atom, a halogen atom, acarboxylate group, an alkoxide group, or an aryloxide group, and where ncan be an integer in the range of from 1 to 3. In one or moreembodiments, each R independently can be a hydrocarbyl group such as,for example, alkyl, cycloalkyl, substituted cycloalkyl, alkenyl,cycloalkenyl, substituted cycloalkenyl, aryl, substituted aryl, aralkyl,alkaryl, allyl, and alkynyl groups, with each group containing in therange of from 1 carbon atom, or the appropriate minimum number of carbonatoms to form the group, up to about 20 carbon atoms. These hydrocarbylgroups may contain heteroatoms including, but not limited to, nitrogen,oxygen, boron, silicon, sulfur, and phosphorus atoms.

Types of the organoaluminum compounds that are represented by thegeneral formula AlR_(n)X_(3-n) include, but are not limited to,trihydrocarbylaluminum, dihydrocarbylaluminum hydride,hydrocarbylaluminum dihydride, dihydrocarbylaluminum carboxylate,hydrocarbylaluminum bis(carboxylate), dihydrocarbylaluminum alkoxide,hydrocarbylaluminum dialkoxide, dihydrocarbylaluminum halide,hydrocarbylaluminum dihalide, dihydrocarbylaluminum aryloxide, andhydrocarbylaluminum diaryloxide compounds. In one embodiment, thealkylating agent can comprise trihydrocarbylaluminum,dihydrocarbylaluminum hydride, and/or hydrocarbylaluminum dihydridecompounds. In one embodiment, when the alkylating agent includes anorganoaluminum hydride compound, the above-mentioned halogen source canbe provided by a tin halide, as disclosed in U.S. Pat. No. 7,008,899,which is incorporated herein by reference in its entirety.

Suitable trihydrocarbylaluminum compounds include, but are not limitedto, trimethylaluminum, triethylaluminum, triisobutylaluminum,tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum,tri-t-butylaluminum, tri-n-pentylaluminum, trineopentylaluminum,tri-n-hexylaluminum, tri-n-octylaluminum, tris(2-ethylhexyl)aluminum,tricyclohexylaluminum, tris(1-methylcyclopentyl)aluminum,triphenylaluminum, tri-p-tolylaluminum,tris(2,6-dimethylphenyl)aluminum, tribenzylaluminum,diethylphenylaluminum, diethyl-p-tolylaluminum, diethylbenzylaluminum,ethyldiphenylaluminum, ethyldi-p-tolylaluminum, andethyldibenzylaluminum.

Suitable dihydrocarbylaluminum hydride compounds include, but are notlimited to, diethylaluminum hydride, di-n-propylaluminum hydride,diisopropylaluminum hydride, di-n-butylaluminum hydride,diisobutylaluminum hydride, di-n-octylaluminum hydride, diphenylaluminumhydride, di-p-tolylaluminum hydride, dibenzylaluminum hydride,phenylethylaluminum hydride, phenyl-n-propylaluminum hydride,phenylisopropylaluminum hydride, phenyl-n-butylaluminum hydride,phenylisobutylaluminum hydride, phenyl-n-octylaluminum hydride,p-tolylethylaluminum hydride, p-tolyl-n-propylaluminum hydride,p-tolylisopropylaluminum hydride, p-tolyl-n-butylaluminum hydride,p-tolylisobutylaluminum hydride, p-tolyl-n-octylaluminum hydride,benzylethylaluminum hydride, benzyl-n-propylaluminum hydride,benzylisopropylaluminum hydride, benzyl-n-butylaluminum hydride,benzylisobutylaluminum hydride, and benzyl-n-octylaluminum hydride.

Suitable hydrocarbylaluminum dihydrides include, but are not limited to,ethylaluminum dihydride, n-propylaluminum dihydride, isopropylaluminumdihydride, n-butylaluminum dihydride, isobutylaluminum dihydride, andn-octylaluminum dihydride.

Suitable dihydrocarbylaluminum halide compounds include, but are notlimited to, diethylaluminum chloride, di-n-propylaluminum chloride,diisopropylaluminum chloride, di-n-butylaluminum chloride,diisobutylaluminum chloride, di-n-octylaluminum chloride,diphenylaluminum chloride, di-p-tolylaluminum chloride, dibenzylaluminumchloride, phenylethylaluminum chloride, phenyl-n-propylaluminumchloride, phenylisopropylaluminum chloride, phenyl-n-butylaluminumchloride, phenylisobutylaluminum chloride, phenyl-n-octylaluminumchloride, p-tolylethylaluminum chloride, p-tolyl-n-propylaluminumchloride, p-tolylisopropylaluminum chloride, p-tolyl-n-butylaluminumchloride, p-tolylisobutylaluminum chloride, p-tolyl-n-octylaluminumchloride, benzylethylaluminum chloride, benzyl-n-propylaluminumchloride, benzylisopropylaluminum chloride, benzyl-n-butylaluminumchloride, benzylisobutylaluminum chloride, and benzyl-n-octylaluminumchloride.

Suitable hydrocarbylaluminum dihalide compounds include, but are notlimited to, ethylaluminum dichloride, n-propylaluminum dichloride,isopropylaluminum dichloride, n-butylaluminum dichloride,isobutylaluminum dichloride, and n-octylaluminum dichloride.

Other organoaluminum compounds useful as alkylating agents that may berepresented by the general formula AlR_(n)X_(3-n) include, but are notlimited to, dimethylaluminum hexanoate, diethylaluminum octoate,diisobutylaluminum 2-ethylhexanoate, dimethylaluminum neodecanoate,diethylaluminum stearate, diisobutylaluminum oleate, methylaluminumbis(hexanoate), ethylaluminum bis(octoate), isobutylaluminumbis(2-ethylhexanoate), methylaluminum bis(neodecanoate), ethylaluminumbis(stearate), isobutylaluminum bis(oleate), dimethylaluminum methoxide,diethylaluminum methoxide, diisobutylaluminum methoxide,dimethylaluminum ethoxide, diethylaluminum ethoxide, diisobutylaluminumethoxide, dimethylaluminum phenoxide, diethylaluminum phenoxide,diisobutylaluminum phenoxide, methylaluminum dimethoxide, ethylaluminumdimethoxide, isobutylaluminum dimethoxide, methylaluminum diethoxide,ethylaluminum diethoxide, isobutylaluminum diethoxide, methylaluminumdiphenoxide, ethylaluminum diphenoxide, and isobutylaluminumdiphenoxide.

Another class of organoaluminum compounds suitable for use as analkylating agent in the present invention is aluminoxanes. Aluminoxanescan comprise oligomeric linear aluminoxanes, which can be represented bythe general formula:

and oligomeric cyclic aluminoxanes, which can be represented by thegeneral formula:

where x can be an integer in the range of from 1 to about 100, or about10 to about 50; y can be an integer in the range of from 2 to about 100,or about 3 to about 20; and where each R independently can be amonovalent organic group that is attached to the aluminum atom via acarbon atom. In one embodiment, each R independently can be ahydrocarbyl group including, but not limited to, alkyl, cycloalkyl,substituted cycloalkyl, alkenyl, cycloalkenyl, substituted cycloalkenyl,aryl, substituted aryl, aralkyl, alkaryl, allyl, and alkynyl groups,with each group containing in the range of from 1 carbon atom, or theappropriate minimum number of carbon atoms to form the group, up toabout 20 carbon atoms. These hydrocarbyl groups may also containheteroatoms including, but not limited to, nitrogen, oxygen, boron,silicon, sulfur, and phosphorus atoms. It should be noted that thenumber of moles of the aluminoxane as used in this application refers tothe number of moles of the aluminum atoms rather than the number ofmoles of the oligomeric aluminoxane molecules. This convention iscommonly employed in the art of catalyst systems utilizing aluminoxanes.

Aluminoxanes can be prepared by reacting trihydrocarbylaluminumcompounds with water. This reaction can be performed according to knownmethods, such as, for example, (1) a method in which thetrihydrocarbylaluminum compound is dissolved in an organic solvent andthen contacted with water, (2) a method in which thetrihydrocarbylaluminum compound is reacted with water of crystallizationcontained in, for example, metal salts, or water adsorbed in inorganicor organic compounds, or (3) a method in which thetrihydrocarbylaluminum compound is reacted with water in the presence ofthe monomer or monomer solution that is to be polymerized.

Suitable aluminoxane compounds include, but are not limited to,methylaluminoxane (“MAO”), modified methylaluminoxane (“MMAO”),ethylaluminoxane, n-propylaluminoxane, isopropylaluminoxane,butylaluminoxane, isobutylaluminoxane, n-pentylaluminoxane,neopentylaluminoxane, n-hexylaluminoxane, n-octylaluminoxane,2-ethylhexylaluminoxane, cyclohexylaluminoxane,1-methylcyclopentylaluminoxane, phenylaluminoxane, and2,6-dimethylphenylaluminoxane. Modified methylaluminoxane can be formedby substituting about 20 to 80 percent of the methyl groups ofmethylaluminoxane with C₂ to C₁₂ hydrocarbyl groups, preferably withisobutyl groups, by using techniques known to those skilled in the art.

Aluminoxanes can be used alone or in combination with otherorganoaluminum compounds. In one embodiment, methylaluminoxane and atleast one other organoaluminum compound (e.g., AlR_(n)X_(3-n)), such asdiisobutyl aluminum hydride, can be employed in combination. U.S.Publication No. 2008/0182954, which is incorporated herein by referencein its entirety, provides other examples where aluminoxanes andorganoaluminum compounds can be employed in combination.

As mentioned above, alkylating agents useful in the present inventioncan comprise organomagnesium compounds. In one or more embodiments,organomagnesium compounds that can be utilized include those representedby the general formula MgR₂, where each R independently can be amonovalent organic group that is attached to the magnesium atom via acarbon atom. In one or more embodiments, each R independently can be ahydrocarbyl group including, but not limited to, alkyl, cycloalkyl,substituted cycloalkyl, alkenyl, cycloalkenyl, substituted cycloalkenyl,aryl, allyl, substituted aryl, aralkyl, alkaryl, and alkynyl groups,with each group containing in the range of from 1 carbon atom, or theappropriate minimum number of carbon atoms to form the group, up toabout 20 carbon atoms. These hydrocarbyl groups may also containheteroatoms including, but not limited to, nitrogen, oxygen, silicon,sulfur, and phosphorus atoms.

Suitable organomagnesium compounds that may be represented by thegeneral formula MgR₂ include, but are not limited to, diethylmagnesium,di-n-propylmagnesium, diisopropylmagnesium, dibutylmagnesium,dihexylmagnesium, diphenylmagnesium, and dibenzylmagnesium.

Another class of organomagnesium compounds that can be utilized as analkylating agent may be represented by the general formula RMgX, where Rcan be a monovalent organic group that is attached to the magnesium atomvia a carbon atom, and X can be a hydrogen atom, a halogen atom, acarboxylate group, an alkoxide group, or an aryloxide group. Where thealkylating agent is an organomagnesium compound that includes a halogenatom, the organomagnesium compound can serve as both the alkylatingagent and at least a portion of the halogen source in the catalystsystems. In one or more embodiments, R can be a hydrocarbyl groupincluding, but not limited to, alkyl, cycloalkyl, substitutedcycloalkyl, alkenyl, cycloalkenyl, substituted cycloalkenyl, aryl,allyl, substituted aryl, aralkyl, alkaryl, and alkynyl groups, with eachgroup containing in the range of from 1 carbon atom, or the appropriateminimum number of carbon atoms to form the group, up to about 20 carbonatoms. These hydrocarbyl groups may also contain heteroatoms including,but not limited to, nitrogen, oxygen, boron, silicon, sulfur, andphosphorus atoms. In one embodiment, X can be a carboxylate group, analkoxide group, or an aryloxide group, with each group containing in therange of from 1 to about 20 carbon atoms.

Types of organomagnesium compounds that may be represented by thegeneral formula RMgX include, but are not limited to,hydrocarbylmagnesium hydride, hydrocarbylmagnesium halide,hydrocarbylmagnesium carboxylate, hydrocarbylmagnesium alkoxide, andhydrocarbylmagnesium aryloxide.

Suitable organomagnesium compounds that may be represented by thegeneral formula RMgX include, but are not limited to, methylmagnesiumhydride, ethylmagnesium hydride, butylmagnesium hydride, hexylmagnesiumhydride, phenylmagnesium hydride, benzylmagnesium hydride,methylmagnesium chloride, ethylmagnesium chloride, butylmagnesiumchloride, hexylmagnesium chloride, phenylmagnesium chloride,benzylmagnesium chloride, methylmagnesium bromide, ethylmagnesiumbromide, butylmagnesium bromide, hexylmagnesium bromide, phenylmagnesiumbromide, benzylmagnesium bromide, methylmagnesium hexanoate,ethylmagnesium hexanoate, butylmagnesium hexanoate, hexylmagnesiumhexanoate, phenylmagnesium hexanoate, benzylmagnesium hexanoate,methylmagnesium ethoxide, ethylmagnesium ethoxide, butylmagnesiumethoxide, hexylmagnesium ethoxide, phenylmagnesium ethoxide,benzylmagnesium ethoxide, methylmagnesium phenoxide, ethylmagnesiumphenoxide, butylmagnesium phenoxide, hexylmagnesium phenoxide,phenylmagnesium phenoxide, and benzylmagnesium phenoxide.

As mentioned above, the catalyst systems employed in the presentinvention can include a halogen source. As used herein, the term halogensource refers to any substance including at least one halogen atom. Inone or more embodiments, at least a portion of the halogen source can beprovided by either of the above-described lanthanide-containing compoundand/or the above-described alkylating agent, when those compoundscontain at least one halogen atom. In other words, thelanthanide-containing compound can serve as both thelanthanide-containing compound and at least a portion of the halogensource. Similarly, the alkylating agent can serve as both the alkylatingagent and at least a portion of the halogen source.

In another embodiment, at least a portion of the halogen source can bepresent in the catalyst systems in the form of a separate and distincthalogen-containing compound. Various compounds, or mixtures thereof,that contain one or more halogen atoms can be employed as the halogensource. Examples of halogen atoms include, but are not limited to,fluorine, chlorine, bromine, and iodine. A combination of two or morehalogen atoms can also be utilized. Halogen-containing compounds thatare soluble in a hydrocarbon solvent are suitable for use in the presentinvention. Hydrocarbon-insoluble halogen-containing compounds, however,can be suspended in a polymerization system to form the catalyticallyactive species, and are therefore also useful.

Useful types of halogen-containing compounds that can be employedinclude, but are not limited to, elemental halogens, mixed halogens,hydrogen halides, organic halides, inorganic halides, metallic halides,and organometallic halides.

Elemental halogens suitable for use in the present invention include,but are not limited to, fluorine, chlorine, bromine, and iodine. Somespecific examples of suitable mixed halogens include iodinemonochloride, iodine monobromide, iodine trichloride, and iodinepentafluoride.

Hydrogen halides include, but are not limited to, hydrogen fluoride,hydrogen chloride, hydrogen bromide, and hydrogen iodide.

Organic halides include, but are not limited to, t-butyl chloride,t-butyl bromide, allyl chloride, allyl bromide, benzyl chloride, benzylbromide, chloro-di-phenylmethane, bromo-di-phenylmethane,triphenylmethyl chloride, triphenylmethyl bromide, benzylidene chloride,benzylidene bromide, methyltrichlorosilane, phenyltrichlorosilane,dimethyldichlorosilane, diphenyldichlorosilane, trimethylchlorosilane,benzoyl chloride, benzoyl bromide, propionyl chloride, propionylbromide, methyl chloroformate, and methyl bromoformate.

Inorganic halides include, but are not limited to, phosphorustrichloride, phosphorus tribromide, phosphorus pentachloride, phosphorusoxychloride, phosphorus oxybromide, boron trifluoride, borontrichloride, boron tribromide, silicon tetrafluoride, silicontetrachloride, silicon tetrabromide, silicon tetraiodide, arsenictrichloride, arsenic tribromide, arsenic triiodide, seleniumtetrachloride, selenium tetrabromide, tellurium tetrachloride, telluriumtetrabromide, and tellurium tetraiodide.

Metallic halides include, but are not limited to, tin tetrachloride, tintetrabromide, aluminum trichloride, aluminum tribromide, antimonytrichloride, antimony pentachloride, antimony tribromide, aluminumtriiodide, aluminum trifluoride, gallium trichloride, galliumtribromide, gallium triiodide, gallium trifluoride, indium trichloride,indium tribromide, indium triiodide, indium trifluoride, titaniumtetrachloride, titanium tetrabromide, titanium tetraiodide, zincdichloride, zinc dibromide, zinc diiodide, and zinc difluoride.

Organometallic halides include, but are not limited to, dimethylaluminumchloride, diethylaluminum chloride, dimethylaluminum bromide,diethylaluminum bromide, dimethylaluminum fluoride, diethylaluminumfluoride, methylaluminum dichloride, ethylaluminum dichloride,methylaluminum dibromide, ethylaluminum dibromide, methylaluminumdifluoride, ethylaluminum difluoride, methylaluminum sesquichloride,ethylaluminum sesquichloride, isobutylaluminum sesquichloride,methylmagnesium chloride, methylmagnesium bromide, methylmagnesiumiodide, ethylmagnesium chloride, ethylmagnesium bromide, butylmagnesiumchloride, butylmagnesium bromide, phenylmagnesium chloride,phenylmagnesium bromide, benzylmagnesium chloride, trimethyltinchloride, trimethyltin bromide, triethyltin chloride, triethyltinbromide, di-t-butyltin dichloride, di-t-butyltin dibromide, dibutyltindichloride, dibutyltin dibromide, tributyltin chloride, and tributyltinbromide.

In one or more embodiments, the above-described catalyst systems cancomprise a compound containing a non-coordinating anion or anon-coordinating anion precursor. In one or more embodiments, a compoundcontaining a non-coordinating anion, or a non-coordinating anionprecursor can be employed in lieu of the above-described halogen source.A non-coordinating anion is a sterically bulky anion that does not formcoordinate bonds with, for example, the active center of a catalystsystem due to steric hindrance. Non-coordinating anions useful in thepresent invention include, but are not limited to, tetraarylborateanions and fluorinated tetraarylborate anions. Compounds containing anon-coordinating anion can also contain a counter cation, such as acarbonium, ammonium, or phosphonium cation. Exemplary counter cationsinclude, but are not limited to, triarylcarbonium cations andN,N-dialkylanilinium cations. Examples of compounds containing anon-coordinating anion and a counter cation include, but are not limitedto, triphenylcarbonium tetrakis(pentafluorophenyl)borate,N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate,triphenylcarbonium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, andN,N-dimethylanilinium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate.

A non-coordinating anion precursor can also be used in this embodiment.A non-coordinating anion precursor is a compound that is able to form anon-coordinating anion under reaction conditions. Usefulnon-coordinating anion precursors include, but are not limited to,triarylboron compounds, BR₃, where R is a strong electron-withdrawingaryl group, such as a pentafluorophenyl or3,5-bis(trifluoromethyl)phenyl group.

The lanthanide-based catalyst composition used in this invention may beformed by combining or mixing the foregoing catalyst ingredients.Although one or more active catalyst species are believed to result fromthe combination of the lanthanide-based catalyst ingredients, the degreeof interaction or reaction between the various catalyst ingredients orcomponents is not known with any great degree of certainty. Therefore,the term “catalyst composition” has been employed to encompass a simplemixture of the ingredients, a complex of the various ingredients that iscaused by physical or chemical forces of attraction, a chemical reactionproduct of the ingredients, or a combination of the foregoing.

The foregoing lanthanide-based catalyst composition may have highcatalytic activity for polymerizing conjugated dienes intocis-1,4-polydienes over a wide range of catalyst concentrations andcatalyst ingredient ratios. Several factors may impact the optimumconcentration of any one of the catalyst ingredients. For example,because the catalyst ingredients may interact to form an active species,the optimum concentration for any one catalyst ingredient may bedependent upon the concentrations of the other catalyst ingredients.

In one or more embodiments, the molar ratio of the alkylating agent tothe lanthanide-containing compound (alkylating agent/Ln) can be variedfrom about 1:1 to about 1,000:1, in other embodiments from about 2:1 toabout 500:1, and in other embodiments from about 5:1 to about 200:1.

In those embodiments where both an aluminoxane and at least one otherorganoaluminum agent are employed as alkylating agents, the molar ratioof the aluminoxane to the lanthanide-containing compound(aluminoxane/Ln) can be varied from 5:1 to about 1,000:1, in otherembodiments from about 10:1 to about 700:1, and in other embodimentsfrom about 20:1 to about 500:1; and the molar ratio of the at least oneother organoaluminum compound to the lanthanide-containing compound(Al/Ln) can be varied from about 1:1 to about 200:1, in otherembodiments from about 2:1 to about 150:1, and in other embodiments fromabout 5:1 to about 100:1.

The molar ratio of the halogen-containing compound to thelanthanide-containing compound is best described in terms of the ratioof the moles of halogen atoms in the halogen source to the moles oflanthanide atoms in the lanthanide-containing compound (halogen/Ln). Inone or more embodiments, the halogen/Ln molar ratio can be varied fromabout 0.5:1 to about 20:1, in other embodiments from about 1:1 to about10:1, and in other embodiments from about 2:1 to about 6:1.

In yet another embodiment, the molar ratio of the non-coordinating anionor non-coordinating anion precursor to the lanthanide-containingcompound (An/Ln) may be from about 0.5:1 to about 20:1, in otherembodiments from about 0.75:1 to about 10:1, and in other embodimentsfrom about 1:1 to about 6:1.

The lanthanide-based catalyst composition can be formed by variousmethods.

In one embodiment, the lanthanide-based catalyst composition may beformed in situ by adding the catalyst ingredients to a solutioncontaining monomer and solvent, or to bulk monomer, in either a stepwiseor simultaneous manner. In one embodiment, the alkylating agent can beadded first, followed by the lanthanide-containing compound, and thenfollowed by the halogen source or by the compound containing anon-coordinating anion or the non-coordinating anion precursor.

In another embodiment, the lanthanide-based catalyst composition may bepreformed. That is, the catalyst ingredients are pre-mixed outside thepolymerization system either in the absence of any monomer or in thepresence of a small amount of at least one conjugated diene monomer atan appropriate temperature, which may be from about −20° C. to about 80°C. The amount of conjugated diene monomer that may be used forpreforming the catalyst can range from about 1 to about 500 moles, inother embodiments from about 5 to about 250 moles, and in otherembodiments from about 10 to about 100 moles per mole of thelanthanide-containing compound. The resulting catalyst composition maybe aged, if desired, prior to being added to the monomer that is to bepolymerized.

In yet another embodiment, the lanthanide-based catalyst composition maybe formed by using a two-stage procedure. The first stage may involvecombining the alkylating agent with the lanthanide-containing compoundeither in the absence of any monomer or in the presence of a smallamount of at least one conjugated diene monomer at an appropriatetemperature, which may be from about −20° C. to about 80° C. The amountof monomer employed in the first stage may be similar to that set forthabove for performing the catalyst. In the second stage, the mixtureformed in the first stage and the halogen source, non-coordinatinganion, or non-coordinating anion precursor can be charged in either astepwise or simultaneous manner to the monomer that is to bepolymerized.

In one or more embodiments, a solvent may be employed as a carrier toeither dissolve or suspend the catalyst in order to facilitate thedelivery of the catalyst to the polymerization system. In otherembodiments, monomer can be used as the carrier. In yet otherembodiments, the catalyst can be used in their neat state without anysolvent.

In one or more embodiments, suitable solvents include those organiccompounds that will not undergo polymerization or incorporation intopropagating polymer chains during the polymerization of monomer in thepresence of the catalyst. In one or more embodiments, these organicspecies are liquid at ambient temperature and pressure. In one or moreembodiments, these organic solvents are inert to the catalyst. Exemplaryorganic solvents include hydrocarbons with a low or relatively lowboiling point such as aromatic hydrocarbons, aliphatic hydrocarbons, andcycloaliphatic hydrocarbons. Non-limiting examples of aromatichydrocarbons include benzene, toluene, xylenes, ethylbenzene,diethylbenzene, and mesitylene. Non-limiting examples of aliphatichydrocarbons include n-pentane, n-hexane, n-heptane, n-octane, n-nonane,n-decane, isopentane, isohexanes, isopentanes, isooctanes,2,2-dimethylbutane, petroleum ether, kerosene, and petroleum spirits.And, non-limiting examples of cycloaliphatic hydrocarbons includecyclopentane, cyclohexane, methylcyclopentane, and methylcyclohexane.Mixtures of the above hydrocarbons may also be used. As is known in theart, aliphatic and cycloaliphatic hydrocarbons may be desirably employedfor environmental reasons. The low-boiling hydrocarbon solvents aretypically separated from the polymer upon completion of thepolymerization.

Other examples of organic solvents include high-boiling hydrocarbons ofhigh molecular weights, including hydrocarbon oils that are commonlyused to oil-extend polymers. Examples of these oils include paraffinicoils, aromatic oils, naphthenic oils, vegetable oils other than castoroils, and low PCA oils including MES, TDAE, SRAE, heavy naphthenic oils.Since these hydrocarbons are non-volatile, they typically do not requireseparation and remain incorporated in the polymer.

The production of the reactive polymer according to this invention canbe accomplished by polymerizing conjugated diene monomer in the presenceof a catalytically effective amount of the coordination catalyst. Theintroduction of the catalyst, the conjugated diene monomer, and anysolvent, if employed, forms a polymerization mixture in which thereactive polymer is formed. The amount of the catalyst to be employedmay depend on the interplay of various factors such as the type ofcatalyst employed, the purity of the ingredients, the polymerizationtemperature, the polymerization rate and conversion desired, themolecular weight desired, and many other factors. Accordingly, aspecific catalyst amount cannot be definitively set forth except to saythat catalytically effective amounts of the catalyst may be used.

In one or more embodiments, the amount of the coordinating metalcompound (e.g., a lanthanide-containing compound) used can be variedfrom about 0.001 to about 2 mmol, in other embodiments from about 0.005to about 1 mmol, and in still other embodiments from about 0.01 to about0.2 mmol per 100 gram of monomer.

In one or more embodiments, the polymerization may be carried out in apolymerization system that includes a substantial amount of solvent. Inone embodiment, a solution polymerization system may be employed inwhich both the monomer to be polymerized and the polymer formed aresoluble in the solvent. In another embodiment, a precipitationpolymerization system may be employed by choosing a solvent in which thepolymer formed is insoluble. In both cases, an amount of solvent inaddition to the amount of solvent that may be used in preparing thecatalyst is usually added to the polymerization system. The additionalsolvent may be the same as or different from the solvent used inpreparing the catalyst. Exemplary solvents have been set forth above. Inone or more embodiments, the solvent content of the polymerizationmixture may be more than 20% by weight, in other embodiments more than50% by weight, and in still other embodiments more than 80% by weightbased on the total weight of the polymerization mixture.

In other embodiments, the polymerization system employed may begenerally considered a bulk polymerization system that includessubstantially no solvent or a minimal amount of solvent. Those skilledin the art will appreciate the benefits of bulk polymerization processes(i.e., processes where monomer acts as the solvent), and therefore thepolymerization system includes less solvent than will deleteriouslyimpact the benefits sought by conducting bulk polymerization. In one ormore embodiments, the solvent content of the polymerization mixture maybe less than about 20% by weight, in other embodiments less than about10% by weight, and in still other embodiments less than about 5% byweight based on the total weight of the polymerization mixture. Inanother embodiment, the polymerization mixture contains no solventsother than those that are inherent to the raw materials employed. Instill another embodiment, the polymerization mixture is substantiallydevoid of solvent, which refers to the absence of that amount of solventthat would otherwise have an appreciable impact on the polymerizationprocess. Polymerization systems that are substantially devoid of solventmay be referred to as including substantially no solvent. In particularembodiments, the polymerization mixture is devoid of solvent.

The polymerization may be conducted in any conventional polymerizationvessels known in the art. In one or more embodiments, solutionpolymerization can be conducted in a conventional stirred-tank reactor.In other embodiments, bulk polymerization can be conducted in aconventional stirred-tank reactor, especially if the monomer conversionis less than about 60%. In still other embodiments, especially where themonomer conversion in a bulk polymerization process is higher than about60%, which typically results in a highly viscous cement, the bulkpolymerization may be conducted in an elongated reactor in which theviscous cement under polymerization is driven to move by piston, orsubstantially by piston. For example, extruders in which the cement ispushed along by a self-cleaning single-screw or double-screw agitatorare suitable for this purpose. Examples of useful bulk polymerizationprocesses are disclosed in U.S. Pat. No. 7,351,776, which isincorporated herein by reference.

In one or more embodiments, all of the ingredients used for thepolymerization can be combined within a single vessel (e.g., aconventional stirred-tank reactor), and all steps of the polymerizationprocess can be conducted within this vessel. In other embodiments, twoor more of the ingredients can be pre-combined in one vessel and thentransferred to another vessel where the polymerization of monomer (or atleast a major portion thereof) may be conducted.

The polymerization can be carried out as a batch process, a continuousprocess, or a semi-continuous process. In the semi-continuous process,the monomer is intermittently charged as needed to replace that monomeralready polymerized. In one or more embodiments, the conditions underwhich the polymerization proceeds may be controlled to maintain thetemperature of the polymerization mixture within a range from about −10°C. to about 200° C., in other embodiments from about 0° C. to about 150°C., and in other embodiments from about 20° C. to about 100° C. In oneor more embodiments, the heat of polymerization may be removed byexternal cooling by a thermally controlled reactor jacket, internalcooling by evaporation and condensation of the monomer through the useof a reflux condenser connected to the reactor, or a combination of thetwo methods. Also, the polymerization conditions may be controlled toconduct the polymerization under a pressure of from about 0.1 atmosphereto about 50 atmospheres, in other embodiments from about 0.5 atmosphereto about 20 atmosphere, and in other embodiments from about 1 atmosphereto about 10 atmospheres. In one or more embodiments, the pressures atwhich the polymerization may be carried out include those that ensurethat the majority of the monomer is in the liquid phase. In these orother embodiments, the polymerization mixture may be maintained underanaerobic conditions.

Some or all of the resulting polymer chains may possess reactive endsbefore the polymerization mixture is quenched. As noted above, thereactive polymer prepared with a coordination catalyst may be referredto as a pseudo-living polymer. In one or more embodiments, apolymerization mixture including reactive polymer may be referred to asan active polymerization mixture. The percentage of polymer chainspossessing a reactive end depends on various factors such as the type ofcatalyst, the type of monomer, the purity of the ingredients, thepolymerization temperature, the monomer conversion, and many otherfactors. In one or more embodiments, at least about 20% of the polymerchains possess a reactive end, in other embodiments at least about 50%of the polymer chains possess a reactive end, and in still otherembodiments at least about 80% of the polymer chains possess a reactiveend. In any event, the reactive polymer can be reacted with a nitrilecompound containing a protected amino group to form the functionalizedpolymer of this invention.

In one or more embodiments, nitrile compounds containing a protectedamino group include those compounds that contain one or more protectedamino groups and one or more cyano groups. For purposes of thisspecification, and for ease of explanation, the nitrile compoundscontaining a protected amino group may be simply referred to as thenitrile compounds.

In one or more embodiments, a cyano group, which may also be referred toas a nitrile group, may be defined by the formula —C≡N.

In one or more embodiments, protected amino groups include those aminogroups that are formed or derived by replacing the two hydrogen atoms ofthe parent amino group (i.e. —NH₂) with other substituents such ashydrocarbyl or silyl groups. Where the protected amino group includes asilyl group and a hydrocarbyl group, the group may be referred to as amonosilylated amino group. Where the protected amino group includes twosilyl groups, the group may be referred to as a disilylated amino group.Where the protected amino group includes two hydrocarbyl groups, thegroup may be referred to as a dihydrocarbylamino group.

Exemplary types of protected amino groups include, but are not limitedto, bis(trihydrocarbylsilyl)amino, bis(dihydrocarbylhydrosilyl)amino,1-aza-disila-1-cyclohydrocarbyl,(trihydrocarbylsilyl)(hydrocarbyl)amino,(dihydrocarbylhydrosilyl)(hydrocarbyl)amino,1-aza-2-sila-1-cyclohydrocarbyl, dihydrocarbylamino, and1-aza-1-cyclohydrocarbyl groups.

Specific examples of bis(trihydrocarbylsilyl)amino groups include, butare not limited to, bis(trimethylsilyl)amino, bis(triethylsilyl)amino,bis(triisopropylsilyl)amino, bis(tri-n-propylsilyl)amino,bis(triisobutylsilyl)amino, bis(tri-t-butylsilyl)amino, andbis(triphenylsilyl)amino groups.

Specific examples of bis(dihydrocarbylhydrosilyl)amino groups include,but are not limited to, bis(dimethylhydrosilyl)amino,bis(diethylhydrosilyl)amino, bis(diisopropylhydrosilyl)amino,bis(di-n-propylhydrosilyl)amino, bis(diisobutylhydrosilyl)amino,bis(di-t-butylhydrosilyl)amino, and bis(diphenylhydrosilyl)amino groups.

Specific examples of 1-aza-disila-1-cyclohydrocarbyl groups include, butare not limited to, 2,2,5,5-tetramethyl-1-aza-2,5-disila-1-cyclopentyl,2,2,5,5-tetraethyl-1-aza-2,5-disila-1-cyclopentyl,2,2,5,5-tetraphenyl-1-aza-2,5-disila-1-cyclopentyl,2,2,6,6-tetramethyl-1-aza-2,6-disila-1-cyclohexyl,2,2,6,6-tetraethyl-1-aza-2,6-disila-1-cyclohexyl, and2,2,6,6-tetraphenyl-1-aza-2,6-disila-1-cyclohexyl groups.

Specific examples of (trihydrocarbylsilyl)(hydrocarbyl)amino groupsinclude, but are not limited to, (trimethylsilyl)(methyl)amino,(triethylsilyl)(methyl)amino, (triphenylsilyl)(methyl)amino,(trimethylsilyl)(ethyl)amino, (triethylsilyl)(phenyl)amino, and(triisopropylsilyl)(methyl)amino groups.

Specific examples of (dihydrocarbylhydrosilyl)(hydrocarbyl)amino groupsinclude, but are not limited to, (dimethylhydrosilyl)(methyl)amino,(diethylhydrosilyl)(methyl)amino, (diisopropylhydrosilyl)(methyl)amino,(di-n-propylhydrosilyl)(ethyl)amino,(diisobutylhydrosilyl)(phenyl)amino,(di-t-butylhydrosilyl)(phenyl)amino, and(diphenylhydrosilyl)(phenyl)amino groups.

Specific examples of 1-aza-2-sila-1-cyclohydrocarbyl groups include, butare not limited to, 2,2-dimethyl-1-aza-2-sila-1-cyclopentyl,2,2-diethyl-1-aza-2-sila-1-cyclopentyl,2,2-diphenyl-1-aza-2-sila-1-cyclopentyl,2,2-diisopropyl-1-aza-2-sila-1-cyclohexyl,2,2-dibutyl-1-aza-2-sila-1-cyclohexyl, and2,2-diphenyl-1-aza-2-sila-1-cyclohexyl groups.

Specific examples of dihydrocarbylamino groups include, but are notlimited to, dimethylamino, diethylamino, di-n-propylamino,diisopropylamino, di-n-butylamino, diisobutylamino, dicyclohexylamino,diphenylamino, dibenzylamino, (methyl)(cyclohexyl)amino,(ethyl)(cyclohexyl)amino, (methyl)(phenyl)amino, (ethyl)(phenyl)amino,(methyl)(benzyl)amino, and (ethyl)(benzyl)amino groups.

Specific examples of 1-aza-1-cyclohydrocarbyl groups include, but arenot limited to, aziridino, azetidino, pyrrolidino, piperidino,homopiperidino, morpholino, N-methylpiperazino, andN-methylhomopiperazino groups.

In one or more embodiments, nitrile compounds containing a protectedamino group may be defined by the formula I:

where R¹ is a divalent organic group, and R² and R³ are eachindependently a monovalent organic group or a hydrolyzable group, or R²and R³ join to form a divalent organic group. In one or moreembodiments, the divalent organic group formed by joining R² and R³ mayinclude one or more hydrolyzable groups. In one or more embodiments,where R² and R³ join to form a divalent organic group, the nitrilecompound containing a protected amino group may be represented by theformula II:

where R¹ and R⁵ are each independently a divalent organic group, and R⁴and R⁶ are each independently a bond or a hydrolyzable group.

In one or more embodiments, mono-valent organic groups may includehydrocarbyl groups or substituted hydrocarbyl groups such as, but notlimited to, alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl, allyl,aralkyl, alkaryl, or alkynyl groups. Substituted hydrocarbyl groupsinclude hydrocarbyl groups in which one or more hydrogen atoms have beenreplaced by a substituent such as an alkyl group. In one or moreembodiments, these groups may include from one, or the appropriateminimum number of carbon atoms to form the group, to about 20 carbonatoms. These groups may also contain heteroatoms such as, but notlimited to, nitrogen, boron, oxygen, silicon, sulfur, tin, andphosphorus atoms.

In one or more embodiments, hydrolyzable groups include those groups orsubstituents that are relatively stable, and therefore remain chemicallybonded to the nitrogen atom, in non-aqueous environments or environmentsthat are devoid or substantially devoid of water. However, once exposedto water, moisture, or materials containing water or moisture, thehydrolyzable groups or substituents hydrolyze and are thereby cleavedfrom the nitrogen atom. As a result, the hydrolyzable groups arereplaced by a hydrogen atom.

Exemplary hydrolyzable groups include trihydrocarbylsilyl anddihydrocarbylhydrosilyl groups. Specific examples of trihydrocarbylsilylgroups include trimethylsilyl, triethylsilyl, tri-n-propylsilyl,triisopropylsilyl, tri-n-butylsilyl, triisobutylsilyl, tri-t-butylsilyl,triphenylsilyl, and t-butyldimethylsilyl groups. Specific examples ofdihydrocarbylhydrosilyl groups include dimethylhydrosilyl,diethylhydrosilyl, di-n-propylhydrosilyl, diisopropylhydrosilyl,di-n-butylhydrosilyl, diisobutylhydrosilyl, di-t-butylhydrosilyl, anddiphenylhydrosilyl groups. A catalyst may also be used to remove thesilyl group from the protected amino group. Suitable catalysts includetetrabutylammonium fluoride, strong acids such as hydrochloric acid, andLewis Acids such as titanium tetrachloride.

In one or more embodiments, divalent organic groups may includehydrocarbylene groups or substituted hydrocarbylene groups such as, butnot limited to, alkylene, cycloalkylene, alkenylene, cycloalkenylene,alkynylene, cycloalkynylene, or arylene groups. Substitutedhydrocarbylene groups include hydrocarbylene groups in which one or morehydrogen atoms have been replaced by a substituent such as an alkylgroup. In one or more embodiments, these groups may include from one, orthe appropriate minimum number of carbon atoms to form the group, toabout 20 carbon atoms. These groups may also contain one or moreheteroatoms such as, but not limited to, nitrogen, oxygen, boron,silicon, sulfur, tin, and phosphorus atoms.

In one or more embodiments, the divalent organic group R¹ is anon-heterocyclic group. In other embodiments, the divalent organic groupR¹ is a heterocyclic group. In one or more embodiments, the divalentorganic group R¹ is an acyclic divalent organic group (either linear orbranched) that may or may not include one or more heteroatoms. In otherembodiments, the divalent organic group R¹ is a cyclic divalent organicgroup that is devoid of heteroatoms. In one or more embodiments, thedivalent organic group R¹ may contain one or more additional protectedamino groups and/or one or more additional cyano groups.

In particular embodiments, R² and R³ of formula I are each independentlya silyl group, and the nitrile compound containing a protected aminogroup may be represented by the formula III:

where R¹ is a divalent organic group, and R⁷ and R⁸ are eachindependently a hydrogen atom or a mono-valent organic group, or atleast one R⁷ and at least one R⁸ join to form a divalent organic group.In one or more embodiments, where an R⁷ and an R⁸ join to form adivalent organic group, the nitrile compound containing a protectedamino group may be represented by the formula IV:

where R¹ and R⁵ are each independently a divalent organic group, and R⁷and R⁸ are each independently a hydrogen atom or a mono-valent organicgroup.

Exemplary types of nitrile compounds that contain a protected aminogroup include those that may derive from nitrile compounds such asarenecarbonitrile compounds, alkanecarbonitrile compounds,alkenecarbonitrile compounds, alkynecarbonitrile compounds,cycloalkanecarbonitrile compounds, cycloalkenecarbonitrile compounds,cycloalkynecarbonitrile compounds, and heterocyclic nitrile compounds.Those skilled in the art appreciate that arenecarbonitrile compoundsinclude arene compounds where one or more hydrogen atoms on the arenecompound have been replaced by cyano groups, and those skilled in theart appreciate that the other classes of nitrile compounds can besimilarly identified.

Exemplary arenecarbonitrile compounds containing a protected amino groupinclude those that derive from arenecarbonitrile compounds such asbenzonitrile, 4-phenylbenzonitrile, 4-methylbenzonitrile,5-indenecarbonitrile, 2-naphthalenecarbonitrile,2,3-naphthalenedicarbonitrile, 9-phenanthrenecarbonitrile,9,10-phenanthrenedicarbonitrile, 9-anthracenecarbonitrile, and1-azulenecarbonitrile.

Exemplary alkanecarbonitrile compounds containing a protected aminogroup include those that derive from alkanecarbonitrile compounds suchas acetonitrile, propionitrile, butyronitrile, isobutyronitrile,valeronitrile, isovaleronitrile, pivalonitrile, 1-hexanenitrile, and1-heptanenitrile.

Exemplary alkenecarbonitrile compounds containing a protected aminogroup include those that derive from alkenecarbonitrile compounds suchas acrylonitrile, methacrylonitrile, crotononitrile, 3-butenenitrile,2-methyl-2-butenenitrile, 2-pentenenitrile, 3-pentenenitrile,4-pentenenitrile, 5-hexenenitrile, 2-methyleneglutaronitrile,6-heptenenitrile, fumaronitrile, methylenemalononitrile, andbenzylidenemalononitrile.

Exemplary alkynecarbonitrile compounds containing a protected aminogroup include those that derive from alkynecarbonitrile compounds suchas 3-butynenitrile, 2-pentynenitrile, 3-pentynenitrile,4-pentynenitrile, and 5-hexynenitrile.

Exemplary cycloalkanecarbonitrile compounds containing a protected aminogroup include those that derive from cycloalkanecarbonitrile compoundssuch as cyclopropanecarbonitrile, cyclobutanecarbonitrile,cyclopentanecarbonitrile, cyclohexanecarbonitrile, andcycloheptanecarbonitrile.

Exemplary cycloalkenecarbonitrile compounds containing a protected aminogroup include those that derive from cycloalkenecarbonitrile compoundssuch as 1-cyclopropenecarbonitrile, 1-cyclobutenecarbonitrile,1-cyclopentenecarbonitrile, 1-cyclohexenecarbonitrile, and1-cycloheptenecarbonitrile.

Exemplary heterocyclic nitrile compounds containing a protected aminogroup include those that derive from heterocyclic nitrile compounds suchas 2-pyridinecarbonitrile, 3-pyridinecarbonitrile,4-pyridinecarbonitrile, 2-pyrimidinecarbonitrile,4-pyrimidinecarbonitrile, 5-pyrimidinecarbonitrile,pyrazinecarbonitrile, 3-pyridazinecarbonitrile, and4-pyridazinecarbonitrile.

Exemplary types of arenecarbonitrile compounds containing a protectedamino group include [bis(trihydrocarbylsilyl)amino]arenecarbonitrile,[bis(dihydrocarbylhydrosilyl)amino]arenecarbonitrile,(1-aza-disila-1-cyclohydrocarbyl)arenecarbonitrile,[(trihydrocarbylsilyl)(hydrocarbyl)amino]arenecarbonitrile,[(dihydrocarbylhydrosilyl)(hydrocarbyl)amino]arenecarbonitrile,(1-aza-2-sila-1-cyclohydrocarbyl)arenecarbonitrile,(dihydrocarbylamino)arenecarbonitrile, and(1-aza-1-cyclohydrocarbyl)arenecarbonitrile.

Exemplary types of alkanecarbonitrile compounds containing a protectedamino group include [bis(trihydrocarbylsilyl)amino]alkanecarbonitrile,[bis(dihydrocarbylhydrosilyl)amino]alkanecarbonitrile,(1-aza-disila-1-cyclohydrocarbyl)alkanecarbonitrile,[(trihydrocarbylsilyl)(hydrocarbyl)amino]alkanecarbonitrile,[(dihydrocarbylhydrosilyl)(hydrocarbyl)amino]alkanecarbonitrile,(1-aza-2-sila-1-cyclohydrocarbyl)alkanecarbonitrile,(dihydrocarbylamino)alkanecarbonitrile, and(1-aza-1-cyclohydrocarbyl)alkanecarbonitrile.

Exemplary types of alkenecarbonitrile compounds containing a protectedamino group include [bis(trihydrocarbylsilyl)amino]alkenecarbonitrile,[bis(dihydrocarbylhydrosilyl)amino]alkenecarbonitrile,(1-aza-disila-1-cyclohydrocarbyl)alkenecarbonitrile,[(trihydrocarbylsilyl)(hydrocarbyl)amino]alkenecarbonitrile,[(dihydrocarbylhydrosilyl)(hydrocarbyl)amino]alkenecarbonitrile,(1-aza-2-sila-1-cyclohydrocarbyl)alkenecarbonitrile,(dihydrocarbylamino)alkenecarbonitrile, and(1-aza-1-cyclohydrocarbyl)alkenecarbonitrile.

Exemplary types of alkynecarbonitrile compounds containing a protectedamino group include [bis(trihydrocarbylsilyl)amino]alkynecarbonitrile,[bis(dihydrocarbylhydrosilyl)amino]alkynecarbonitrile,(1-aza-disila-1-cyclohydrocarbyl)alkynecarbonitrile,[(trihydrocarbylsilyl)(hydrocarbyl)amino]alkynecarbonitrile,[(dihydrocarbylhydrosilyl)(hydrocarbyl)amino]alkynecarbonitrile,(1-aza-2-sila-1-cyclohydrocarbyl)alkynecarbonitrile,(dihydrocarbylamino)alkynecarbonitrile, and(1-aza-1-cyclohydrocarbyl)alkynecarbonitrile.

Exemplary types of cycloalkanecarbonitrile compounds containing aprotected amino group include[bis(trihydrocarbylsilyl)amino]cycloalkanecarbonitrile,[bis(dihydrocarbylhydrosilyl)amino]cycloalkanecarbonitrile,(1-aza-disila-1-cyclohydrocarbyl)cycloalkanecarbonitrile,[(trihydrocarbylsilyl)(hydrocarbyl)amino]cycloalkanecarbonitrile,[(dihydrocarbylhydrosilyl)(hydrocarbyl)amino]cycloalkanecarbonitrile,(1-aza-2-sila-1-cyclohydrocarbyl)cycloalkanecarbonitrile,(dihydrocarbylamino)cycloalkanecarbonitrile, and(1-aza-1-cyclohydrocarbyl)cycloalkanecarbonitrile.

Exemplary types of cycloalkenecarbonitrile compounds containing aprotected amino group include[bis(trihydrocarbylsilyl)amino]cycloalkenecarbonitrile,[bis(dihydrocarbylhydrosilyl)amino]cycloalkenecarbonitrile,(1-aza-disila-1-cyclohydrocarbyl)cycloalkenecarbonitrile,[(trihydrocarbylsilyl)(hydrocarbyl)amino]cycloalkenecarbonitrile,[(dihydrocarbylhydrosilyl)(hydrocarbyl)amino]cycloalkenecarbonitrile,(1-aza-2-sila-1-cyclohydrocarbyl)cycloalkenecarbonitrile,(dihydrocarbylamino)cycloalkenecarbonitrile, and(1-aza-1-cyclohydrocarbyl)cycloalkenecarbonitrile.

Exemplary types of cycloalkynecarbonitrile compounds containing aprotected amino group include[bis(trihydrocarbylsilyl)amino]cycloalkynecarbonitrile,[bis(dihydrocarbylhydrosilyl)amino]cycloalkynecarbonitrile,(1-aza-disila-1-cyclohydrocarbyl)cycloalkynecarbonitrile,[(trihydrocarbylsilyl)(hydrocarbyl)amino]cycloalkynecarbonitrile,[(dihydrocarbylhydrosilyl)(hydrocarbyl)amino]cycloalkynecarbonitrile,(1-aza-2-sila-1-cyclohydrocarbyl)cycloalkynecarbonitrile,(dihydrocarbylamino)cycloalkynecarbonitrile, and(1-aza-1-cyclohydrocarbyl)cycloalkynecarbonitrile.

Exemplary types of heterocyclic nitrile compounds containing a protectedamino group include [bis(trihydrocarbylsilyl)amino]heterocyclic nitrile,[bis(dihydrocarbylhydrosilyl)amino]heterocyclic nitrile,(1-aza-disila-1-cyclohydrocarbyl)heterocyclic nitrile,[(trihydrocarbylsilyl)(hydrocarbyl)amino]heterocyclic nitrile,[(dihydrocarbylhydrosilyl)(hydrocarbyl)amino]heterocyclic nitrile,(1-aza-2-sila-1-cyclohydrocarbyl)heterocyclic nitrile,(dihydrocarbylamino)heterocyclic nitrile, and(1-aza-1-cyclohydrocarbyl)heterocyclic nitrile.

Specific examples of arenecarbonitrile compounds containing a protectedamino group include 2-[bis(trimethylsilyl)amino]benzonitrile,3-[bis(trimethylsilyl)amino]benzonitrile,4-[bis(trimethylsilyl)amino]benzonitrile,2-[bis(trimethylsilyl)aminomethyl]benzonitrile,3-[bis(trimethylsilyl)aminomethyl]benzonitrile,4-[bis(trimethylsilyl)aminomethyl]benzonitrile,2-(2,2,5,5-tetramethyl-1-aza-2,5-disila-1-cyclopentyl)benzonitrile,3-(2,2,5,5-tetramethyl-1-aza-2,5-disila-1-cyclopentyl)benzonitrile,4-(2,2,5,5-tetramethyl-1-aza-2,5-disila-1-cyclopentyl)benzonitrile,2-[(2,2,5,5-tetramethyl-1-aza-2,5-disila-1-cyclopentyl)methyl]benzonitrile,3-[(2,2,5,5-tetramethyl-1-aza-2,5-disila-1-cyclopentyl)methyl]benzonitrile,4-[(2,2,5,5-tetramethyl-1-aza-2,5-disila-1-cyclopentyl)methyl]benzonitrile,2-[(trimethylsilyl)(methyl)amino]benzonitrile,3-[(trimethylsilyl)(methyl)amino]benzonitrile,4-[(trimethylsilyl)(methyl)amino]benzonitrile,2-[(trimethylsilyl)(methyl)aminomethyl]benzonitrile,3-[(trimethylsilyl)(methyl)aminomethyl]benzonitrile,4-[(trimethylsilyl)(methyl)aminomethyl]benzonitrile,2-(2,2-dimethyl-1-aza-2-sila-1-cyclopentyl)benzonitrile,3-(2,2-dimethyl-1-aza-2-sila-1-cyclopentyl)benzonitrile,4-(2,2-dimethyl-1-aza-2-sila-1-cyclopentyl)benzonitrile,2-[(2,2-dimethyl-1-aza-2-sila-1-cyclopentyl)methyl]benzonitrile,3-[(2,2-dimethyl-1-aza-2-sila-1-cyclopentyl)methyl]benzonitrile,4-[(2,2-dimethyl-1-aza-2-sila-1-cyclopentyl)methyl]benzonitrile,2-(dimethylamino)benzonitrile, 3-(dimethylamino)benzonitrile,4-(dimethylamino)benzonitrile, 4-(diethylamino)benzonitrile,4-(di-n-propylamino)benzonitrile, 4-(diisopropylamino)benzonitrile,4-(di-n-butylamino)benzonitrile, 4-(diisobutylamino)benzonitrile,4-(dicyclohexylamino)benzonitrile, 4-(diphenylamino)benzonitrile,4-(dibenzylamino)benzonitrile,4-[(methyl)(cyclohexyl)amino]benzonitrile,4-[(ethyl)(cyclohexyl)amino]benzonitrile,4-[(methyl)(phenyl)amino]benzonitrile,4-[(ethyl)(phenyl)amino]benzonitrile,4-[(methyl)(benzyl)amino]benzonitrile,4-[(ethyl)(benzyl)amino]benzonitrile,2-(dimethylaminomethyl)benzonitrile,3-(dimethylaminomethyl)benzonitrile,4-(dimethylaminomethyl)benzonitrile, 4-aziridinobenzonitrile,4-azetidinobenzonitrile, 4-pyrrolidinobenzonitrile,4-piperidinobenzonitrile, 4-homopiperidinobenzonitrile,4-morpholinobenzonitrile, 4-(N-methylpiperazino)benzonitrile,4-(N-methylhomopiperazino)benzonitrile, 4-(aziridinomethyl)benzonitrile,4-(azetidinomethyl)benzonitrile, 4-(pyrrolidinomethyl)benzonitrile,4-(piperidinomethyl)benzonitrile, 4-(homopiperidinomethyl)benzonitrile,4-(morpholinomethyl)benzonitrile,4-[(N-methylpiperazino)methyl]benzonitrile, and4-[(N-methylhomopiperazino)methyl]benzonitrile

Specific examples of alkanecarbonitrile compounds containing a protectedamino group include [bis(trimethylsilyl)amino]acetonitrile,3-[bis(trimethylsilyl)amino]propionitrile,4-[bis(trimethylsilyl)amino]butyronitrile,5-[bis(trimethylsilyl)amino]valeronitrile,(2,2,5,5-tetramethyl-1-aza-2,5-disila-1-cyclopentyl)acetonitrile,3-(2,2,5,5-tetramethyl-1-aza-2,5-disila-1-cyclopentyl)propionitrile,4-(2,2,5,5-tetramethyl-1-aza-2,5-disila-1-cyclopentyl)butyronitrile,5-(2,2,5,5-tetramethyl-1-aza-2,5-disila-1-cyclopentyl)valeronitrile,[(trimethylsilyl)(methyl)amino]acetonitrile,[(trimethylsilyl)(ethyl)amino]acetonitrile,3-[(trimethylsilyl)(methyl)amino]propionitrile,3-[(trimethylsilyl)(ethyl)amino]propionitrile,4-[(trimethylsilyl)(methyl)amino]butyronitrile,4-[(trimethylsilyl)(ethyl)amino]butyronitrile,5-[(trimethylsilyl)(methyl)amino]valeronitrile,5-[(trimethylsilyl)(ethyl)amino]valeronitrile,N-trimethylsilyl-3,3′-iminodipropionitrile,N-trimethylsilyliminodiacetonitrile,(2,2-dimethyl-1-aza-2-sila-1-cyclopentyl)acetonitrile,3-(2,2-dimethyl-1-aza-2-sila-1-cyclopentyl)propionitrile,4-(2,2-dimethyl-1-aza-2-sila-1-cyclopentyl)butyronitrile,5-(2,2-dimethyl-1-aza-2-sila-1-cyclopentyl)valeronitrile,(dimethylamino)acetonitrile, (diethylamino)acetonitrile,(diphenylamino)acetonitrile, 3-(dimethylamino)propionitrile,3-(diethylamino)propionitrile, 3-(di-n-propylamino)propionitrile,3-(diisopropylamino)propionitrile, 3-(di-n-butylamino)propionitrile,3-(diisobutylamino)propionitrile, 3-(dicyclohexylamino)propionitrile,3-(diphenylamino)propionitrile, 3-[bis(cyanoethyl)amino]propionitrile,3-(dibenzylamino)propionitrile,3-[(methyl)(cyclohexyl)amino]propionitrile,3-[(ethyl)(cyclohexyl)amino]propionitrile,3-[(methyl)(phenyl)amino]propionitrile,3-[(ethyl)(phenyl)amino]propionitrile,3-[(methyl)(benzyl)amino]propionitrile,3-[(ethyl)(benzyl)amino]propionitrile, 4-(dimethylamino)butyronitrile,4-(diethylamino)butyronitrile, 4-(di-n-propylamino)butyronitrile,4-(diisopropylamino)butyronitrile, 4-(di-n-butylamino)butyronitrile,4-(diisobutylamino)butyronitrile, 4-(dicyclohexylamino)butyronitrile,4-(diphenylamino)butyronitrile, 4-(dibenzylamino)butyronitrile,4-[(methyl)(cyclohexyl)amino]butyronitrile,4-[(ethyl)(cyclohexyl)amino]butyronitrile,4-[(methyl)(phenyl)amino]butyronitrile,4-[(ethyl)(phenyl)amino]butyronitrile,4-[(methyl)(benzyl)amino]butyronitrile,4-[(ethyl)(benzyl)amino]butyronitrile, 5-(dimethylamino)valeronitrile,5-(diethylamino)valeronitrile, 5-(diphenylamino)valeronitrile,aziridinoacetonitrile, azetidinoacetonitrile, pyrrolidinoacetonitrile,piperidinoacetonitrile, homopiperidinoacetonitrile,morpholinoacetonitrile, (N-methylpiperazino)acetonitrile,(N-methylhomopiperazino)acetonitrile, 3-aziridinopropionitrile,3-azetidinopropionitrile, 3-pyrrolidinopropionitrile,3-piperidinopropionitrile, 3-homopiperidinopropionitrile,3-morpholinopropionitrile, 3-(N-methylpiperazino)propionitrile,3-(N-methylhomopiperazino)propionitrile, 4-aziridinobutyronitrile,4-azetidinobutyronitrile, 4-pyrrolidinobutyronitrile,4-piperidinobutyronitrile, 4-homopiperidinobutyronitrile,4-morpholinobutyronitrile, 4-(N-methylpiperazino)butyronitrile,4-(N-methylhomopiperazino)butyronitrile, 5-aziridinovaleronitrile,5-azetidinovaleronitrile, 5-pyrrolidinovaleronitrile,5-piperidinovaleronitrile, 5-homopiperidinovaleronitrile,5-morpholinovaleronitrile, 5-(N-methylpiperazino)valeronitrile, and5-(N-methylhomopiperazino)valeronitrile.

Specific examples of alkenecarbonitrile compounds containing a protectedamino group include 3-[bis(trimethylsilyl)amino]crotononitrile,3-[bis(trimethylsilyl)amino]-4-pentenenitrile,3-[bis(trimethylsilyl)amino]-5-hexenenitrile,3-(2,2,5,5-tetramethyl-1-aza-2,5-disila-1-cyclopentyl)crotononitrile,3-(2,2,5,5-tetramethyl-1-aza-2,5-disila-1-cyclopentyl)-4-pentenenitrile,3-(2,2,5,5-tetramethyl-1-aza-2,5-disila-1-cyclopentyl)-5-hexenenitrile,3-[(trimethylsilyl)(methyl)amino]crotononitrile,3-[(trimethylsilyl)(ethyl)amino]crotononitrile,3-[(trimethylsilyl)(methyl)amino]-4-pentenenitrile,3-[(trimethylsilyl)(ethyl)amino]-4-pentenenitrile,3-[(trimethylsilyl)(methyl)amino]-5-hexenenitrile,3-[(trimethylsilyl)(ethyl)amino]-5-hexenenitrile,3-(2,2-dimethyl-1-aza-2-sila-1-cyclopentyl)crotononitrile,3-(2,2-dimethyl-1-aza-2-sila-1-cyclopentyl)-4-pentenenitrile,3-(2,2-dimethyl-1-aza-2-sila-1-cyclopentyl)-5-hexenenitrile,3-(dimethylamino)acrylonitrile, 3-(dimethylamino)crotononitrile,3-(diethylamino)crotononitrile, 3-(di-n-propylamino)crotononitrile,3-(diisopropylamino)crotononitrile, 3-(di-n-butylamino)crotononitrile,3-(diisobutylamino)crotononitrile, 3-(dicyclohexylamino)crotononitrile,3-(diphenylamino)crotononitrile, 3-(dibenzylamino)crotononitrile,3-[(methyl)(cyclohexyl)amino]crotononitrile,3-[(ethyl)(cyclohexyl)amino]crotononitrile,3-[(methyl)(phenyl)amino]crotononitrile,3-[(ethyl)(phenyl)amino]crotononitrile,3-[(methyl)(benzyl)amino]crotononitrile,3-[(ethyl)(benzyl)amino]crotononitrile,3-(dimethylamino)-4-pentenenitrile, 3-(diethylamino)-4-pentenenitrile,3-(di-n-propylamino)-4-pentenenitrile,3-(diisopropylamino)-4-pentenenitrile,3-(di-n-butylamino)-4-pentenenitrile,3-(diisobutylamino)-4-pentenenitrile,3-(dicyclohexylamino)-4-pentenenitrile,3-(diphenylamino)-4-pentenenitrile, 3-(dibenzylamino)-4-pentenenitrile,3-[(methyl)(cyclohexyl)amino]-4-pentenenitrile,3-[(ethyl)(cyclohexyl)amino]-4-pentenenitrile,3-[(methyl)(phenyl)amino]-4-pentenenitrile,3-[(ethyl)(phenyl)amino]-4-pentenenitrile,3-[(methyl)(benzyl)amino]-4-pentenenitrile,3-[(ethyl)(benzyl)amino]-4-pentenenitrile,3-(dimethylamino)-5-hexenenitrile, 3-(diethylamino)-5-hexenenitrile,3-(di-n-propylamino)-5-hexenenitrile,3-(diisopropylamino)-5-hexenenitrile,3-(di-n-butylamino)-5-hexenenitrile,3-(diisobutylamino)-5-hexenenitrile,3-(dicyclohexylamino)-5-hexenenitrile,3-(diphenylamino)-5-hexenenitrile, 3-(dibenzylamino)-5-hexenenitrile,3-[(methyl)(cyclohexyl)amino]-5-hexenenitrile,3-[(ethyl)(cyclohexyl)amino]-5-hexenenitrile,3-[(methyl)(phenyl)amino]-5-hexenenitrile,3-[(ethyl)(phenyl)amino]-5-hexenenitrile,3-[(methyl)(benzyl)amino]-5-hexenenitrile,3-[(ethyl)(benzyl)amino]-5-hexenenitrile, 3-aziridinocrotononitrile,3-azetidinocrotononitrile, 3-pyrrolidinocrotononitrile,3-piperidinocrotononitrile, 3-homopiperidinocrotononitrile,3-morpholinocrotononitrile, 3-(N-methylpiperazino)crotononitrile,3-(N-methylhomopiperazino)crotononitrile, 3-aziridino-4-pentenenitrile,3-azetidino-4-pentenenitrile, 3-pyrrolidino-4-pentenenitrile,3-piperidino-4-pentenenitrile, 3-homopiperidino-4-pentenenitrile,3-morpholino-4-pentenenitrile, 3-(N-methylpiperazino)-4-pentenenitrile,3-(N-methylhomopiperazino)-4-pentenenitrile,3-aziridino-5-hexenenitrile, 3-azetidino-5-hexenenitrile,3-pyrrolidino-5-hexenenitrile, 3-piperidino-5-hexenenitrile,3-homopiperidino-5-hexenenitrile, 3-morpholino-5-hexenenitrile,3-(N-methylpiperazino)-5-hexenenitrile, and3-(N-methylhomopiperazino)-5-hexenenitrile.

Specific alkynecarbonitrile compounds containing protected amino groupsinclude 3-[bis(trimethylsilyl)amino]-4-pentynenitrile,3-[bis(trimethylsilyl)amino]-5-hexynenitrile,3-(2,2,5,5-tetramethyl-1-aza-2,5-disila-1-cyclopentyl)-4-pentynenitrile,3-(2,2,5,5-tetramethyl-1-aza-2,5-disila-1-cyclopentyl)-5-hexynenitrile,3-[(trimethylsilyl)(methyl)amino]-4-pentynenitrile,3-[(trimethylsilyl)(ethyl)amino]-4-pentynenitrile,3-[(trimethylsilyl)(methyl)amino]-5-hexynenitrile,3-[(trimethylsilyl)(ethyl)amino]-5-hexynenitrile,3-(2,2-dimethyl-1-aza-2-sila-1-cyclopentyl)-4-pentynenitrile,3-(2,2-dimethyl-1-aza-2-sila-1-cyclopentyl)-5-hexynenitrile,3-(dimethylamino)-4-pentynenitrile, 3-(diethylamino)-4-pentynenitrile,3-(di-n-propylamino)-4-pentynenitrile,3-(diisopropylamino)-4-pentynenitrile,3-(di-n-butylamino)-4-pentynenitrile,3-(diisobutylamino)-4-pentynenitrile,3-(dicyclohexylamino)-4-pentynenitrile,3-(diphenylamino)-4-pentynenitrile, 3-(dibenzylamino)-4-pentynenitrile,3-[(methyl)(cyclohexyl)amino]-4-pentynenitrile,3-[(ethyl)(cyclohexyl)amino]-4-pentynenitrile,3-[(methyl)(phenyl)amino]-4-pentynenitrile,3-[(ethyl)(phenyl)amino]-4-pentynenitrile,3-[(methyl)(benzyl)amino]-4-pentynenitrile,3-[(ethyl)(benzyl)amino]-4-pentynenitrile,3-(dimethylamino)-5-hexynenitrile, 3-(diethylamino)-5-hexynenitrile,3-(di-n-propylamino)-5-hexynenitrile,3-(diisopropylamino)-5-hexynenitrile,3-(di-n-butylamino)-5-hexynenitrile,3-(diisobutylamino)-5-hexynenitrile,3-(dicyclohexylamino)-5-hexynenitrile,3-(diphenylamino)-5-hexynenitrile, 3-(dibenzylamino)-5-hexynenitrile,3-[(methyl)(cyclohexyl)amino]-5-hexynenitrile,3-[(ethyl)(cyclohexyl)amino]-5-hexynenitrile,3-[(methyl)(phenyl)amino]-5-hexynenitrile,3-[(ethyl)(phenyl)amino]-5-hexynenitrile,3-[(methyl)(benzyl)amino]-5-hexynenitrile,3-[(ethyl)(benzyl)amino]-5-hexynenitrile, 3-aziridino-4-pentynenitrile,3-azetidino-4-pentynenitrile, 3-pyrrolidino-4-pentynenitrile,3-piperidino-4-pentynenitrile, 3-homopiperidino-4-pentynenitrile,3-morpholino-4-pentynenitrile, 3-(N-methylpiperazino)-4-pentynenitrile,3-(N-methylhomopiperazino)-4-pentynenitrile,3-aziridino-5-hexynenitrile, 3-azetidino-5-hexynenitrile,3-pyrrolidino-5-hexynenitrile, 3-piperidino-5-hexynenitrile,3-homopiperidino-5-hexynenitrile, 3-morpholino-5-hexynenitrile,3-(N-methylpiperazino)-5-hexynenitrile, and3-(N-methylhomopiperazino)-5-hexynenitrile.

Specific examples of cycloalkanecarbonitrile compounds containing aprotected amino group include3-[bis(trimethylsilyl)amino]cyclopentanecarbonitrile,4-[bis(trimethylsilyl)amino]cyclohexanecarbonitrile,3-(2,2,5,5-tetramethyl-1-aza-2,5-disila-1-cyclopentyl)cyclopentanecarbonitrile,4-(2,2,5,5-tetramethyl-1-aza-2,5-disila-1-cyclopentyl)cyclohexanecarbonitrile,3-[(trimethylsilyl)(methyl)amino]cyclopentanecarbonitrile,3-[(trimethylsilyl)(ethyl)amino]cyclopentanecarbonitrile,4-[(trimethylsilyl)(methyl)amino]cyclohexanecarbonitrile,4-[(trimethylsilyl)(ethyl)amino]cyclohexanecarbonitrile,3-(2,2-dimethyl-1-aza-2-sila-1-cyclopentyl)cyclopentanecarbonitrile,4-(2,2-dimethyl-1-aza-2-sila-1-cyclopentyl)cyclohexanecarbonitrile,3-(3-dimethylaminophenyl)cyclopropane-1,1,2,2-tetracarbonitrile,3-(dimethylamino)cyclopentanecarbonitrile,3-(diethylamino)cyclopentanecarbonitrile,3-(di-n-propylamino)cyclopentanecarbonitrile,3-(diisopropylamino)cyclopentanecarbonitrile,3-(di-n-butylamino)cyclopentanecarbonitrile,3-(diisobutylamino)cyclopentanecarbonitrile,3-(dicyclohexylamino)cyclopentanecarbonitrile,3-(diphenylamino)cyclopentanecarbonitrile,3-(dibenzylamino)cyclopentanecarbonitrile,3-[(methyl)(cyclohexyl)amino]cyclopentanecarbonitrile,3-[(ethyl)(cyclohexyl)amino]cyclopentanecarbonitrile,3-[(methyl)(phenyl)amino]cyclopentanecarbonitrile,3-[(ethyl)(phenyl)amino]cyclopentanecarbonitrile,3-[(methyl)(benzyl)amino]cyclopentanecarbonitrile,3-[(ethyl)(benzyl)amino]cyclopentanecarbonitrile,4-(dimethylamino)cyclohexanecarbonitrile,4-(diethylamino)cyclohexanecarbonitrile,4-(di-n-propylamino)cyclohexanecarbonitrile,4-(diisopropylamino)cyclohexanecarbonitrile,4-(di-n-butylamino)cyclohexanecarbonitrile,4-(diisobutylamino)cyclohexanecarbonitrile,3-(dicyclohexylamino)cyclohexanecarbonitrile,4-(diphenylamino)cyclohexanecarbonitrile,4-(dibenzylamino)cyclohexanecarbonitrile,4-[(methyl)(cyclohexyl)amino]cyclohexanecarbonitrile,4-[(ethyl)(cyclohexyl)amino]cyclohexanecarbonitrile,4-[(methyl)(phenyl)amino]cyclohexanecarbonitrile,4-[(ethyl)(phenyl)amino]cyclohexanecarbonitrile,4-[(methyl)(benzyl)amino]cyclohexanecarbonitrile,4-[(ethyl)(benzyl)amino]cyclohexanecarbonitrile,4-aziridinocyclopentanecarbonitrile,3-azetidinocyclopentanecarbonitrile,3-pyrrolidinocyclopentanecarbonitrile,3-piperidinocyclopentanecarbonitrile,3-homopiperidinocyclopentanecarbonitrile,3-morpholinocyclopentanecarbonitrile,3-(N-methylpiperazino)cyclopentanecarbonitrile,3-(N-methylhomopiperazino)cyclopentanecarbonitrile,4-aziridinocyclohexanecarbonitrile, 4-azetidinocyclohexanecarbonitrile,4-pyrrolidinocyclohexanecarbonitrile,4-piperidinocyclohexanecarbonitrile,4-homopiperidinocyclohexanecarbonitrile,4-morpholinocyclohexanecarbonitrile,4-(N-methylpiperazino)cyclohexanecarbonitrile, and4-(N-methylhomopiperazino)cyclohexanecarbonitrile.

Specific examples of cycloalkenecarbonitrile compounds containing aprotected amino group include4-[bis(trimethylsilyl)amino]cyclopentene-1-carbonitrile,4-[bis(trimethylsilyl)amino]cyclohexene-1-carbonitrile,4-(2,2,5,5-tetramethyl-1-aza-2,5-disila-1-cyclopentyl)cyclopentene-1-carbonitrile,4-(2,2,5,5-tetramethyl-1-aza-2,5-disila-1-cyclopentyl)cyclohexene-1-carbonitrile,4-[(trimethylsilyl)(methyl)amino]cyclopentene-1-carbonitrile,4-[(trimethylsilyl)(ethyl)amino]cyclopentene-1-carbonitrile,4-[(trimethylsilyl)(methyl)amino]cyclohexene-1-carbonitrile,4-[(trimethylsilyl)(ethyl)amino]cyclohexene-1-carbonitrile,4-(2,2-dimethyl-1-aza-2-sila-1-cyclopentyl)cyclopentene-1-carbonitrile,4-(2,2-dimethyl-1-aza-2-sila-1-cyclopentyl)cyclohexene-1-carbonitrile,4-(dimethylamino)cyclopentene-1-carbonitrile,4-(diethylamino)cyclopentene-1-carbonitrile,4-(di-n-propylamino)cyclopentene-1-carbonitrile,4-(diisopropylamino)cyclopentene-1-carbonitrile,4-(di-n-butylamino)cyclopentene-1-carbonitrile,4-(diisobutylamino)cyclopentene-1-carbonitrile,4-(dicyclohexylamino)cyclopentene-1-carbonitrile,4-(diphenylamino)cyclopentene-1-carbonitrile,4-(dibenzylamino)cyclopentene-1-carbonitrile,4-[(methyl)(cyclohexyl)amino]cyclopentene-1-carbonitrile,4-[(ethyl)(cyclohexyl)amino]cyclopentene-1-carbonitrile,4-[(methyl)(phenyl)amino]cyclopentene-1-carbonitrile,4-[(ethyl)(phenyl)amino]cyclopentene-1-carbonitrile,4-[(methyl)(benzyl)amino]cyclopentene-1-carbonitrile,4-[(ethyl)(benzyl)amino]cyclopentene-1-carbonitrile,4-(dimethylamino)cyclohexene-1-carbonitrile,4-(diethylamino)cyclohexene-1-carbonitrile,4-(di-n-propylamino)cyclohexene-1-carbonitrile,4-(diisopropylamino)cyclohexene-1-carbonitrile,4-(di-n-butylamino)cyclohexene-1-carbonitrile,4-(diisobutylamino)cyclohexene-1-carbonitrile,4-(dicyclohexylamino)cyclohexene-1-carbonitrile,4-(diphenylamino)cyclohexene-1-carbonitrile,4-(dibenzylamino)cyclohexene-1-carbonitrile,4-[(methyl)(cyclohexyl)amino]cyclohexene-1-carbonitrile,4-[(ethyl)(cyclohexyl)amino]cyclohexene-1-carbonitrile,4-[(methyl)(phenyl)amino]cyclohexene-1-carbonitrile,4-[(ethyl)(phenyl)amino]cyclohexene-1-carbonitrile,4-[(methyl)(benzyl)amino]cyclohexene-1-carbonitrile,4-[(ethyl)(benzyl)amino]cyclohexene-1-carbonitrile,4-aziridinocyclopentene-1-carbonitrile,4-azetidinocyclopentene-1-carbonitrile,4-pyrrolidinocyclopentene-1-carbonitrile,4-piperidinocyclopentene-1-carbonitrile,4-homopiperidinocyclopentene-1-carbonitrile,4-morpholinocyclopentene-1-carbonitrile,4-(N-methylpiperazino)cyclopentene-1-carbonitrile,4-(N-methylhomopiperazino)cyclopentene-1-carbonitrile,4-aziridinocyclohexene-1-carbonitrile,4-azetidinocyclohexene-1-carbonitrile,4-pyrrolidinocyclohexene-1-carbonitrile,4-piperidinocyclohexene-1-carbonitrile,4-homopiperidinocyclohexene-1-carbonitrile,4-morpholinocyclohexene-1-carbonitrile,4-(N-methylpiperazino)cyclohexene-1-carbonitrile, and4-(N-methylhomopiperazino)cyclohexene-1-carbonitrile.

Specific examples of heterocyclic nitrile compounds containing aprotected amino group include5-[bis(trimethylsilyl)amino]-2-pyridinecarbonitrile,5-[bis(trimethylsilyl)amino]-2-pyrimidinecarbonitrile,5-(2,2,5,5-tetramethyl-1-aza-2,5-disila-1-cyclopentyl)-2-pyridinecarbonitrile,5-(2,2,5,5-tetramethyl-1-aza-2,5-disila-1-cyclopentyl)-2-pyrimidinecarbonitrile,5-[(trimethylsilyl)(methyl)amino]-2-pyridinecarbonitrile,5-[(trimethylsilyl)(ethyl)amino]-2-pyridinecarbonitrile,5-[(trimethylsilyl)(methyl)amino]-2-pyrimidinecarbonitrile,5-[(trimethylsilyl)(ethyl)amino]-2-pyrimidinecarbonitrile,5-(2,2-dimethyl-1-aza-2-sila-1-cyclopentyl)-2-pyridinecarbonitrile,5-(2,2-dimethyl-1-aza-2-sila-1-cyclopentyl)-2-pyrimidinecarbonitrile,5-(dimethylamino)-2-pyridinecarbonitrile,3-(diethylamino)-2-pyridinecarbonitrile,5-(di-n-propylamino)-2-pyridinecarbonitrile,5-(diisopropylamino)-2-pyridinecarbonitrile,5-(di-n-butylamino)-2-pyridinecarbonitrile,5-(diisobutylamino)-2-pyridinecarbonitrile,5-(dicyclohexylamino)-2-pyridinecarbonitrile,5-(diphenylamino)-2-pyridinecarbonitrile,5-(dibenzylamino)-2-pyridinecarbonitrile,5-[(methyl)(cyclohexyl)amino]-2-pyridinecarbonitrile,5-[(ethyl)(cyclohexyl)amino]-2-pyridinecarbonitrile,5-[(methyl)(phenyl)amino]-2-pyridinecarbonitrile,5-[(ethyl)(phenyl)amino]-2-pyridinecarbonitrile,5-[(methyl)(benzyl)amino]-2-pyridinecarbonitrile,5-[(ethyl)(benzyl)amino]-2-pyridinecarbonitrile,5-(dimethylamino)-2-pyrimidinecarbonitrile,5-(diethylamino)-2-pyrimidinecarbonitrile,5-(di-n-propylamino)-2-pyrimidinecarbonitrile,5-(diisopropylamino)-2-pyrimidinecarbonitrile,5-(di-n-butylamino)-2-pyrimidinecarbonitrile,5-(diisobutylamino)-2-pyrimidinecarbonitrile,5-(dicyclohexylamino)-2-pyrimidinecarbonitrile,5-(diphenylamino)-2-pyrimidinecarbonitrile,5-(dibenzylamino)-2-pyrimidinecarbonitrile,5-[(methyl)(cyclohexyl)amino]-2-pyrimidinecarbonitrile,5-[(ethyl)(cyclohexyl)amino]-2-pyrimidinecarbonitrile,5-[(methyl)(phenyl)amino]-2-pyrimidinecarbonitrile,5-[(ethyl)(phenyl)amino]-2-pyrimidinecarbonitrile,5-[(methyl)(benzyl)amino]-2-pyrimidinecarbonitrile,5-[(ethyl)(benzyl)amino]-2-pyrimidinecarbonitrile,5-aziridino-2-pyridinecarbonitrile, 5-azetidino-2-pyridinecarbonitrile,5-pyrrolidino-2-pyridinecarbonitrile,5-piperidino-2-pyridinecarbonitrile,5-homopiperidino-2-pyridinecarbonitrile,5-morpholino-2-pyridinecarbonitrile,5-(N-methylpiperazino)-2-pyridinecarbonitrile,5-(N-methylhomopiperazino)-2-pyridinecarbonitrile,5-aziridino-2-pyrimidinecarbonitrile,5-azetidino-2-pyrimidinecarbonitrile,5-pyrrolidino-2-pyrimidinecarbonitrile,5-piperidino-2-pyrimidinecarbonitrile,5-homopiperidino-2-pyrimidinecarbonitrile,5-morpholino-2-pyrimidinecarbonitrile,5-(N-methylpiperazino)-2-pyrimidinecarbonitrile, and5-(N-methylhomopiperazino)-2-pyrimidinecarbonitrile.

In one or more embodiments, the nitrile compounds containing a protectedamino group can be synthesized by alkylating or silylating a nitrilecompound containing a primary amino group (i.e. —NH₂) or a secondaryamino group represented by the formula —NH(R), where R is a mono-valentorganic group such as a hydrocarbyl or silyl group. Exemplary alkylatingreagents include alkyl halides. Exemplary silylating reagents includetrialkylsilyl halides, 1,2-bis(chlorodimethylsilyl)ethane, andtrialkylsilyl trifluoromethanesulfonate. A base such as triethylaminemay be used to neutralize the acid formed during the alkylation orsilylation reaction.

The amount of the nitrile compound containing a protected amino groupthat can be added to the polymerization mixture to yield thefunctionalized polymer of this invention may depend on various factorsincluding the type and amount of catalyst used to synthesize thereactive polymer and the desired degree of functionalization. In one ormore embodiments, where the reactive polymer is prepared by employing alanthanide-based catalyst, the amount of the nitrile compound employedcan be described with reference to the lanthanide metal of thelanthanide-containing compound. For example, the molar ratio of thenitrile compound to the lanthanide metal may be from about 1:1 to about200:1, in other embodiments from about 5:1 to about 150:1, and in otherembodiments from about 10:1 to about 100:1.

In one or more embodiments, in addition to the nitrile compoundcontaining a protected amino group, a co-functionalizing agent may alsobe added to the polymerization mixture to yield a functionalized polymerwith tailored properties. A mixture of two or more co-functionalizingagents may also be employed. The co-functionalizing agent may be addedto the polymerization mixture prior to, together with, or after theintroduction of the nitrile compound. In one or more embodiments, theco-functionalizing agent is added to the polymerization mixture at least5 minutes after, in other embodiments at least 10 minutes after, and inother embodiments at least 30 minutes after the introduction of thenitrile compound.

In one or more embodiments, co-functionalizing agents include compoundsor reagents that can react with a reactive polymer produced by thisinvention and thereby provide the polymer with a functional group thatis distinct from a propagating chain that has not been reacted with theco-functionalizing agent. The functional group may be reactive orinteractive with other polymer chains (propagating and/ornon-propagating) or with other constituents such as reinforcing fillers(e.g. carbon black) that may be combined with the polymer. In one ormore embodiments, the reaction between the co-functionalizing agent andthe reactive polymer proceeds via an addition or substitution reaction.

Useful co-functionalizing agents may include compounds that simplyprovide a functional group at the end of a polymer chain without joiningtwo or more polymer chains together, as well as compounds that cancouple or join two or more polymer chains together via a functionallinkage to form a single macromolecule. The latter type ofco-functionalizing agents may also be referred to as coupling agents.

In one or more embodiments, co-functionalizing agents include compoundsthat will add or impart a heteroatom to the polymer chain. In particularembodiments, co-functionalizing agents include those compounds that willimpart a functional group to the polymer chain to form a functionalizedpolymer that reduces the 50° C. hysteresis loss of a carbon-black filledvulcanizates prepared from the functionalized polymer as compared tosimilar carbon-black filled vulcanizates prepared fromnon-functionalized polymer. In one or more embodiments, this reductionin hysteresis loss is at least 5%, in other embodiments at least 10%,and in other embodiments at least 15%.

In one or more embodiments, suitable co-functionalizing agents includethose compounds that contain groups that may react with the reactivepolymers produced in accordance with this invention. Exemplaryco-functionalizing agents include ketones, quinones, aldehydes, amides,esters, isocyanates, isothiocyanates, epoxides, imines, aminoketones,aminothioketones, and acid anhydrides. Examples of these compounds aredisclosed in U.S. Pat. Nos. 4,906,706, 4,990,573, 5,064,910, 5,567,784,5,844,050, 6,838,526, 6,977,281, 6,992,147, 7,642,322, 7,671,136,7,750,087, and 7,294,680; Japanese Patent Application Nos. 05-051406A,05-059103A, 10-306113A, and 11-035633A; which are incorporated herein byreference. Other examples of co-functionalizing agents include azinecompounds as described in U.S. Pat. No. 7,879,952, hydrobenzamidecompounds as disclosed in U.S. Ser. No. 11/710,713, nitro compounds asdisclosed in U.S. Pat. No. 7,671,138, and protected oxime compounds asdisclosed in U.S. Pat. No. 8,088,868 and U.S. Publication No. U.S.2012-0077941 A1, all of which are incorporated herein by reference.

In particular embodiments, the co-functionalizing agents employed may bemetal halides, metalloid halides, alkoxysilanes, metal carboxylates,hydrocarbylmetal carboxylates, hydrocarbylmetal ester-carboxylates, andmetal alkoxides.

Exemplary metal halide compounds include tin tetrachloride, tintetrabromide, tin tetraiodide, n-butyltin trichloride, phenyltintrichloride, di-n-butyltin dichloride, diphenyltin dichloride,tri-n-butyltin chloride, triphenyltin chloride, germanium tetrachloride,germanium tetrabromide, germanium tetraiodide, n-butylgermaniumtrichloride, di-n-butylgermanium dichloride, and tri-n-butylgermaniumchloride.

Exemplary metalloid halide compounds include silicon tetrachloride,silicon tetrabromide, silicon tetraiodide, methyltrichlorosilane,phenyltrichlorosilane, dimethyldichlorosilane, diphenyldichlorosilane,boron trichloride, boron tribromide, boron triiodide, phosphoroustrichloride, phosphorous tribromide, and phosphorus triiodide.

In one or more embodiments, the alkoxysilanes may include at least onegroup selected from the group consisting of an epoxy group and anisocyanate group.

Exemplary alkoxysilane compounds including an epoxy group include(3-glycidyloxypropyl)trimethoxysilane,(3-glycidyloxypropyl)triethoxysilane,(3-glycidyloxypropyl)triphenoxysilane,(3-glycidyloxypropyl)methyldimethoxysilane,(3-glycidyloxypropyl)methyldiethoxysilane,(3-glycidyloxypropyl)methyldiphenoxysilane,[2-(3,4-epoxycyclohexyl)ethyl]trimethoxysilane, and[2-(3,4-epoxycyclohexyl)ethyl]triethoxysilane.

Exemplary alkoxysilane compounds including an isocyanate group include(3-isocyanatopropyl)trimethoxysilane,(3-isocyanatopropyl)triethoxysilane,(3-isocyanatopropyl)triphenoxysilane,(3-isocyanatopropyl)methyldimethoxysilane,(3-isocyanatopropyl)methyldiethoxysilane(3-isocyanatopropyl)methyldiphenoxysilane, and(isocyanatomethyl)methyldimethoxysilane.

Exemplary metal carboxylate compounds include tin tetraacetate, tinbis(2-ethylhexanaote), and tin bis(neodecanoate).

Exemplary hydrocarbylmetal carboxylate compounds include triphenyltin2-ethylhexanoate, tri-n-butyltin 2-ethylhexanoate, tri-n-butyltinneodecanoate, triisobutyltin 2-ethylhexanoate, diphenyltinbis(2-ethylhexanoate), di-n-butyltin bis(2-ethylhexanoate),di-n-butyltin bis(neodecanoate), phenyltin tris(2-ethylhexanoate), andn-butylltin tris(2-ethylhexanoate).

Exemplary hydrocarbylmetal ester-carboxylate compounds includedi-n-butyltin bis(n-octylmaleate), di-n-octyltin bis(n-octylmaleate),diphenyltin bis(n-octylmaleate), di-n-butyltin bis(2-ethylhexylmaleate),di-n-octyltin bis(2-ethylhexylmaleate), and diphenyltinbis(2-ethylhexylmaleate).

Exemplary metal alkoxide compounds include dimethoxytin, diethoxytin,tetraethoxytin, tetra-n-propoxytin, tetraisopropoxytin,tetra-n-butoxytin, tetraisobutoxytin, tetra-t-butoxytin, andtetraphenoxytin.

The amount of the co-functionalizing agent that can be added to thepolymerization mixture may depend on various factors including the typeand amount of catalyst used to synthesize the reactive polymer and thedesired degree of functionalization. In one or more embodiments, wherethe reactive polymer is prepared by employing a lanthanide-basedcatalyst, the amount of the co-functionalizing agent employed can bedescribed with reference to the lanthanide metal of thelanthanide-containing compound. For example, the molar ratio of theco-functionalizing agent to the lanthanide metal may be from about 1:1to about 200:1, in other embodiments from about 5:1 to about 150:1, andin other embodiments from about 10:1 to about 100:1.

The amount of the co-functionalizing agent employed can also bedescribed with reference to the nitrile compound containing a protectedamino group. In one or more embodiments, the molar ratio of theco-functionalizing agent to the nitrile compound may be from about0.05:1 to about 1:1, in other embodiments from about 0.1:1 to about0.8:1, and in other embodiments from about 0.2:1 to about 0.6:1.

In one or more embodiments, the nitrile compound containing a protectedamino group (and optionally the co-functionalizing agent) may beintroduced to the polymerization mixture at a location (e.g., within avessel) where the polymerization has been conducted. In otherembodiments, the nitrile compound may be introduced to thepolymerization mixture at a location that is distinct from where thepolymerization has taken place. For example, the nitrile compound may beintroduced to the polymerization mixture in downstream vessels includingdownstream reactors or tanks, in-line reactors or mixers, extruders, ordevolatilizers.

In one or more embodiments, the nitrile compound containing a protectedamino group (and optionally the co-functionalizing agent) can be reactedwith the reactive polymer after a desired monomer conversion is achievedbut before the polymerization mixture is quenched by a quenching agent.In one or more embodiments, the reaction between the nitrile compoundand the reactive polymer may take place within 30 minutes, in otherembodiments within 5 minutes, and in other embodiments within one minuteafter the peak polymerization temperature is reached. In one or moreembodiments, the reaction between the nitrile compound and the reactivepolymer can occur once the peak polymerization temperature is reached.In other embodiments, the reaction between the nitrile compound and thereactive polymer can occur after the reactive polymer has been stored.In one or more embodiments, the storage of the reactive polymer occursat room temperature or below room temperature under an inert atmosphere.In one or more embodiments, the reaction between the nitrile compoundand the reactive polymer may take place at a temperature from about 10°C. to about 150° C., and in other embodiments from about 20° C. to about100° C. The time required for completing the reaction between thenitrile compound and the reactive polymer depends on various factorssuch as the type and amount of the catalyst used to prepare the reactivepolymer, the type and amount of the nitrile compound, as well as thetemperature at which the functionalization reaction is conducted. In oneor more embodiments, the reaction between the nitrile compound and thereactive polymer can be conducted for about 10 to 60 minutes.

In one or more embodiments, after the reaction between the reactivepolymer and the nitrile compound containing a protected amino group (andoptionally the co-functionalizing agent) has been accomplished orcompleted, a quenching agent can be added to the polymerization mixturein order to protonate the reaction product between the reactive polymerand the nitrile compound, inactivate any residual reactive polymerchains, and/or inactivate the catalyst or catalyst components. Thequenching agent may include a protic compound, which includes, but isnot limited to, an alcohol, a carboxylic acid, an inorganic acid, water,or a mixture thereof. An antioxidant such as2,6-di-tert-butyl-4-methylphenol may be added along with, before, orafter the addition of the quenching agent. The amount of the antioxidantemployed may be in the range of 0.2% to 1% by weight of the polymerproduct. Additionally, the polymer product can be oil extended by addingan oil to the polymer, which may be in the form of a polymer cement orpolymer dissolved or suspended in monomer. Practice of the presentinvention does not limit the amount of oil that may be added, andtherefore conventional amounts may be added (e.g., 5-50 phr). Usefuloils or extenders that may be employed include, but are not limited to,aromatic oils, paraffinic oils, naphthenic oils, vegetable oils otherthan castor oils, low PCA oils including MES, TDAE, and SRAE, and heavynaphthenic oils.

Once the polymerization mixture has been quenched, the variousconstituents of the polymerization mixture may be recovered. In one ormore embodiments, the unreacted monomer can be recovered from thepolymerization mixture. For example, the monomer can be distilled fromthe polymerization mixture by using techniques known in the art. In oneor more embodiments, a devolatilizer may be employed to remove themonomer from the polymerization mixture. Once the monomer has beenremoved from the polymerization mixture, the monomer may be purified,stored, and/or recycled back to the polymerization process.

The polymer product may be recovered from the polymerization mixture byusing techniques known in the art. In one or more embodiments,desolventization and drying techniques may be used. For instance, thepolymer can be recovered by passing the polymerization mixture through aheated screw apparatus, such as a desolventizing extruder, in which thevolatile substances are removed by evaporation at appropriatetemperatures (e.g., about 100° C. to about 170° C.) and underatmospheric or sub-atmospheric pressure. This treatment serves to removeunreacted monomer as well as any low-boiling solvent. Alternatively, thepolymer can also be recovered by subjecting the polymerization mixtureto steam desolventization, followed by drying the resulting polymercrumbs in a hot air tunnel. The polymer can also be recovered bydirectly drying the polymerization mixture on a drum dryer.

While the reactive polymer and the nitrile compound containing aprotected amino group (and optionally the co-functionalizing agent) arebelieved to react to produce a novel functionalized polymer, which canbe protonated or further modified, the exact chemical structure of thefunctionalized polymer produced in every embodiment is not known withany great degree of certainty, particularly as the structure relates tothe residue imparted to the polymer chain end by the nitrile compoundand optionally the co-functionalizing agent. Indeed, it is speculatedthat the structure of the functionalized polymer may depend upon variousfactors such as the conditions employed to prepare the reactive polymer(e.g., the type and amount of the catalyst) and the conditions employedto react the nitrile compound (and optionally the co-functionalizingagent) with the reactive polymer (e.g., the types and amounts of thenitrile compound and the co-functionalizing agent).

In one or more embodiments, one of the products resulting from thereaction between the reactive polymer and the nitrile compoundcontaining a protected amino group, particularly after reaction with aquenching agent, may be a functionalized polymer defined by the formula:

where π is a cis-1,4-polydiene chain having a cis-1,4-linkage contentthat is greater than 60%, R¹ is a divalent organic group, and R² and R³are each independently a mono-valent organic group or a hydrolyzablegroup, or R² and R³ join to form a divalent organic group.

It is believed that the functionalized polymers described by the aboveformula may, upon exposure to moisture, be converted to functionalizedpolymers defined by the formula:

where π is a cis-1,4-polydiene chain having a cis-1,4-linkage contentthat is greater than 60%, R¹ is a divalent organic group, and R² and R³are each independently a mono-valent organic group or a hydrogen atom,or R² and R³ join to form a divalent organic group.

In one or more embodiments, the functionalized polymers preparedaccording to this invention may contain unsaturation. In these or otherembodiments, the functionalized polymers are vulcanizable. In one ormore embodiments, the functionalized polymers can have a glasstransition temperature (T_(g)) that is less than 0° C., in otherembodiments less than −20° C., and in other embodiments less than −30°C. In one embodiment, these polymers may exhibit a single glasstransition temperature. In particular embodiments, the polymers may behydrogenated or partially hydrogenated.

In one or more embodiments, the functionalized polymers of thisinvention may be cis-1,4-polydienes having a cis-1,4-linkage contentthat is greater than 60%, in other embodiments greater than about 75%,in other embodiments greater than about 90%, and in other embodimentsgreater than about 95%, where the percentages are based upon the numberof diene mer units adopting the cis-1,4 linkage versus the total numberof diene merunits. Also, these polymers may have a 1,2-linkage contentthat is less than about 7%, in other embodiments less than 5%, in otherembodiments less than 2%, and in other embodiments less than 1%, wherethe percentages are based upon the number of diene mer units adoptingthe 1,2-linkage versus the total number of diene merunits. The balanceof the diene merunits may adopt the trans-1,4-linkage. The cis-1,4-,1,2-, and trans-1,4-linkage contents can be determined by infraredspectroscopy. The number average molecular weight (M_(n)) of thesepolymers may be from about 1,000 to about 1,000,000, in otherembodiments from about 5,000 to about 200,000, in other embodiments fromabout 25,000 to about 150,000, and in other embodiments from about50,000 to about 120,000, as determined by using gel permeationchromatography (GPC) calibrated with polystyrene standards andMark-Houwink constants for the polymer in question. The molecular weightdistribution or polydispersity (M_(w)/M_(n)) of these polymers may befrom about 1.5 to about 5.0, and in other embodiments from about 2.0 toabout 4.0.

Advantageously, the functionalized polymers of this invention mayexhibit improved cold-flow resistance and provide rubber compositionsthat demonstrate reduced hysteresis. The functionalized polymers areparticularly useful in preparing rubber compositions that can be used tomanufacture tire components. Rubber compounding techniques and theadditives employed therein are generally disclosed in The Compoundingand Vulcanization of Rubber, in Rubber Technology (2^(nd) Ed. 1973).

The rubber compositions can be prepared by using the functionalizedpolymers alone or together with other elastomers (i.e., polymers thatcan be vulcanized to form compositions possessing rubbery or elastomericproperties). Other elastomers that may be used include natural andsynthetic rubbers. The synthetic rubbers typically derive from thepolymerization of conjugated diene monomers, the copolymerization ofconjugated diene monomers with other monomers such as vinyl-substitutedaromatic monomers, or the copolymerization of ethylene with one or moreα-olefins and optionally one or more diene monomers.

Exemplary elastomers include natural rubber, synthetic polyisoprene,polybutadiene, polyisobutylene-co-isoprene, neoprene,poly(ethylene-co-propylene), poly(styrene-co-butadiene),poly(styrene-co-isoprene), poly(styrene-co-isoprene-co-butadiene),poly(isoprene-co-butadiene), poly(ethylene-co-propylene-co-diene),polysulfide rubber, acrylic rubber, urethane rubber, silicone rubber,epichlorohydrin rubber, and mixtures thereof. These elastomers can havea myriad of macromolecular structures including linear, branched, andstar-shaped structures.

The rubber compositions may include fillers such as inorganic andorganic fillers. Examples of organic fillers include carbon black andstarch. Examples of inorganic fillers include silica, aluminumhydroxide, magnesium hydroxide, mica, talc (hydrated magnesiumsilicate), and clays (hydrated aluminum silicates). Carbon blacks andsilicas are the most common fillers used in manufacturing tires. Incertain embodiments, a mixture of different fillers may beadvantageously employed.

In one or more embodiments, carbon blacks include furnace blacks,channel blacks, and lamp blacks. More specific examples of carbon blacksinclude super abrasion furnace blacks, intermediate super abrasionfurnace blacks, high abrasion furnace blacks, fast extrusion furnaceblacks, fine furnace blacks, semi-reinforcing furnace blacks, mediumprocessing channel blacks, hard processing channel blacks, conductingchannel blacks, and acetylene blacks.

In particular embodiments, the carbon blacks may have a surface area(EMSA) of at least 20 m²/g and in other embodiments at least 35 m²/g;surface area values can be determined by ASTM D-1765 using thecetyltrimethylammonium bromide (CTAB) technique. The carbon blacks maybe in a pelletized form or an unpelletized flocculent form. Thepreferred form of carbon black may depend upon the type of mixingequipment used to mix the rubber compound.

The amount of carbon black employed in the rubber compositions can be upto about 50 parts by weight per 100 parts by weight of rubber (phr),with about 5 to about 40 phr being typical.

Some commercially available silicas which may be used include Hi-Sil™215, Hi-Sil™ 233, and Hi-Sil™ 190 (PPG Industries, Inc.; Pittsburgh,Pa.). Other suppliers of commercially available silica include GraceDavison (Baltimore, Md.), Degussa Corp. (Parsippany, N.J.), RhodiaSilica Systems (Cranbury, N.J.), and J.M. Huber Corp. (Edison, N.J.).

In one or more embodiments, silicas may be characterized by theirsurface areas, which give a measure of their reinforcing character. TheBrunauer, Emmet and Teller (“BET”) method (described in J. Am. Chem.Soc., vol. 60, p. 309 et seq.) is a recognized method for determiningthe surface area. The BET surface area of silica is generally less than450 m²/g. Useful ranges of surface area include from about 32 to about400 m²/g, about 100 to about 250 m²/g, and about 150 to about 220 m²/g.

The pH's of the silicas are generally from about 5 to about 7 orslightly over 7, or in other embodiments from about 5.5 to about 6.8.

In one or more embodiments, where silica is employed as a filler (aloneor in combination with other fillers), a coupling agent and/or ashielding agent may be added to the rubber compositions during mixing inorder to enhance the interaction of silica with the elastomers. Usefulcoupling agents and shielding agents are disclosed in U.S. Pat. Nos.3,842,111, 3,873,489, 3,978,103, 3,997,581, 4,002,594, 5,580,919,5,583,245, 5,663,396, 5,674,932, 5,684,171, 5,684,172 5,696,197,6,608,145, 6,667,362, 6,579,949, 6,590,017, 6,525,118, 6,342,552, and6,683,135, which are incorporated herein by reference.

The amount of silica employed in the rubber compositions can be fromabout 1 to about 100 phr or in other embodiments from about 5 to about80 phr. The useful upper range is limited by the high viscosity impartedby silicas. When silica is used together with carbon black, the amountof silica can be decreased to as low as about 1 phr; as the amount ofsilica is decreased, lesser amounts of coupling agents and shieldingagents can be employed. Generally, the amounts of coupling agents andshielding agents range from about 4% to about 20% based on the weight ofsilica used.

A multitude of rubber curing agents (also called vulcanizing agents) maybe employed, including sulfur or peroxide-based curing systems. Curingagents are described in Kirk-Othmer, ENCYCLOPEDIA OF CHEMICALTECHNOLOGY, Vol. 20, pgs. 365-468, (3^(rd) Ed. 1982), particularlyVulcanization Agents and Auxiliary Materials, pgs. 390-402, and A. Y.Coran, Vulcanization, ENCYCLOPEDIA OF POLYMER SCIENCE AND ENGINEERING,(2^(nd) Ed. 1989), which are incorporated herein by reference.Vulcanizing agents may be used alone or in combination.

Other ingredients that are typically employed in rubber compounding mayalso be added to the rubber compositions. These include accelerators,accelerator activators, oils, plasticizer, waxes, scorch inhibitingagents, processing aids, zinc oxide, tackifying resins, reinforcingresins, fatty acids such as stearic acid, peptizers, and antidegradantssuch as antioxidants and antiozonants. In particular embodiments, theoils that are employed include those conventionally used as extenderoils, which are described above.

All ingredients of the rubber compositions can be mixed with standardmixing equipment such as Banbury or Brabender mixers, extruders,kneaders, and two-rolled mills. In one or more embodiments, theingredients are mixed in two or more stages. In the first stage (oftenreferred to as the masterbatch mixing stage), a so-called masterbatch,which typically includes the rubber component and filler, is prepared.To prevent premature vulcanization (also known as scorch), themasterbatch may exclude vulcanizing agents. The masterbatch may be mixedat a starting temperature of from about 25° C. to about 125° C. with adischarge temperature of about 135° C. to about 180° C. Once themasterbatch is prepared, the vulcanizing agents may be introduced andmixed into the masterbatch in a final mixing stage, which is typicallyconducted at relatively low temperatures so as to reduce the chances ofpremature vulcanization. Optionally, additional mixing stages, sometimescalled remills, can be employed between the masterbatch mixing stage andthe final mixing stage. One or more remill stages are often employedwhere the rubber composition includes silica as the filler. Variousingredients including the functionalized polymers of this invention canbe added during these remills.

The mixing procedures and conditions particularly applicable tosilica-filled tire formulations are described in U.S. Pat. Nos.5,227,425, 5,719,207, and 5,717,022, as well as European Patent No.890,606, all of which are incorporated herein by reference. In oneembodiment, the initial masterbatch is prepared by including thefunctionalized polymer of this invention and silica in the substantialabsence of coupling agents and shielding agents.

The rubber compositions prepared from the functionalized polymers ofthis invention are particularly useful for forming tire components suchas treads, subtreads, sidewalls, body ply skims, bead filler, and thelike. Preferably, the functional polymers of this invention are employedin tread and sidewall formulations. In one or more embodiments, thesetread or sidewall formulations may include from about 10% to about 100%by weight, in other embodiments from about 35% to about 90% by weight,and in other embodiments from about 50% to about 80% by weight of thefunctionalized polymer based on the total weight of the rubber withinthe formulation.

Where the rubber compositions are employed in the manufacture of tires,these compositions can be processed into tire components according toordinary tire manufacturing techniques including standard rubbershaping, molding and curing techniques. Typically, vulcanization iseffected by heating the vulcanizable composition in a mold; e.g., it maybe heated to about 140° C. to about 180° C. Cured or crosslinked rubbercompositions may be referred to as vulcanizates, which generally containthree-dimensional polymeric networks that are thermoset. The otheringredients, such as fillers and processing aids, may be evenlydispersed throughout the crosslinked network. Pneumatic tires can bemade as discussed in U.S. Pat. Nos. 5,866,171, 5,876,527, 5,931,211, and5,971,046, which are incorporated herein by reference.

In order to demonstrate the practice of the present invention, thefollowing examples have been prepared and tested. The examples shouldnot, however, be viewed as limiting the scope of the invention. Theclaims will serve to define the invention.

EXAMPLES Example 1 Synthesis of3-[Bis(trimethylsilyl)amino]propionitrile (3-BTMSAPN)

About 5.04 g of 3-aminopropionitrile, 16.01 g of triethylamine, and 10ml of toluene were mixed in a round-bottom reaction flask cooled with anice bath. To this mixture was added, in a dropwise fashion, a solutionof 35.16 g of trimethylsilyl trifluoromethanesulfonate in 50 ml oftoluene. The resulting mixture was stirred at room temperature for 2days to give a biphasic mixture. The top layer was transferred toanother flask, and the bottom layer was extracted with 50 ml of toluene.The combined toluene solution was evaporated under vacuum. The residuewas extracted with 100 ml of hexane, and the hexane layer was evaporatedunder vacuum, yielding 3-[bis(trimethylsilyl)amino]propionitrile(3-BTMSAPN) as a white solid (13.86 g, 90% yield). The ¹H NMR data(C₆D₆, 25° C., referenced to tetramethylsilane) of the product arelisted as follows: δ 2.65 (triplet, 2H, CH₂ protons), 1.59 (triplet, 2H,CH₂ protons), −0.05 (singlet, 18H, Si—CH₃ protons). From the ¹H NMRdata, the structure of the product was determined to be as follows:

Example 2 Synthesis of 4-[Bis(trimethylsilyl)aminomethyl]benzonitrile(4-BTMSAMBZN)

About 5.20 g of 4-(aminomethyl)benzonitrile hydrochloride, 10.30 g oftriethylamine, and 10 ml of toluene were mixed in a round-bottomreaction flask cooled with an ice bath. To this mixture was added, in adropwise fashion, a solution of 15.1 g of trimethylsilyltrifluoromethanesulfonate in 50 ml of toluene. The resulting mixture wasstirred at room temperature for 3 days to give a biphasic mixture. Thetop layer was transferred to another flask, and the bottom layer wasextracted with 40 ml of toluene. The combined toluene solution wasevaporated under vacuum. The residue was extracted with 100 ml ofhexane, and the hexane layer was evaporated under vacuum, yielding4-[bis(trimethylsilyl)aminomethyl]benzonitrile (4-BTMSAMBZN) as a whitesolid (8.12 g, 95% yield). The ¹H NMR data (C₆D₆, 25° C., referenced totetramethylsilane) of the product are listed as follows: δ 7.00(doublet, 2H, aromatic protons), 6.83 (doublet, 2H, aromatic protons),3.72 (singlet, 2H, CH₂ protons), −0.06 (singlet, 18H, Si—CH₃ protons).From the ¹H NMR data, the structure of the product was determined to beas follows:

Example 3 Synthesis of 3-[Bis(trimethylsilyl)amino]benzonitrile(3-BTMSABZN)

About 5.87 g of 3-aminobenzonitrile, 11.57 g of triethylamine, and 10 mlof toluene were mixed in a round-bottom reaction flask cooled with anice bath. To this mixture was added, in a dropwise fashion, a solutionof 25.41 g of trimethylsilyl trifluoromethanesulfonate in 50 ml oftoluene. The resulting mixture was heated to reflux for 12 hours to givea biphasic mixture. The top layer was transferred to another flask, andthe bottom layer was extracted with 40 ml of toluene. The combinedtoluene solution was evaporated under vacuum. The residue was extractedwith 100 ml of hexane, and the hexane layer was evaporated under vacuum,yielding 3-[bis(trimethylsilyl)amino]benzonitrile (3-BTMSABZN) as abrown oil (12.62 g, 97% yield). The ¹H NMR data (C₆D₆, 25° C.,referenced to tetramethylsilane) of the product are listed as follows: δ7.00 (multiplet, 1H, aromatic proton), 6.81 (multiplet, 1H, aromaticproton), 6.67 (multiplet, 1H, aromatic proton), 6.59 (multiplet, 1H,aromatic proton), −0.10 (singlet, 18H, Si—CH₃ protons). From the ¹H NMRdata, the structure of the product was determined to be as follows:

Example 4 Synthesis of 4-[Bis(trimethylsilyl)amino]benzonitrile(4-BTMSABZN)

About 5.09 g of 4-aminobenzonitrile, 10.03 g of triethylamine, and 10 mlof toluene were mixed in a round-bottom reaction flask cooled with anice bath. To this mixture was added, in a dropwise fashion, a solutionof 22.02 g of trimethylsilyl trifluoromethanesulfonate in 50 ml oftoluene. The resulting mixture was heated to reflux for 40 hours to givea biphasic mixture. The top layer was transferred to another flask, andthe bottom layer was extracted with 40 ml of toluene. The combinedtoluene solution was evaporated under vacuum. The residue was extractedwith 100 ml of hexane, and the hexane layer was evaporated under vacuum,yielding 4-[bis(trimethylsilyl)amino]benzonitrile (4-BTMSABZN) as abrown oil (10.77 g, 95% yield). The ¹H NMR data (C₆D₆, 25° C.,referenced to tetramethylsilane) of the product are listed as follows: δ6.93 (doublet, 2H, aromatic protons), 6.43 (doublet, 2H, aromaticprotons), −0.07 (singlet, 18H, Si—CH₃ protons). From the ¹H NMR data,the structure of the product was determined to be as follows:

Example 5 Synthesis of5-[Bis(trimethylsilyl)amino]-2-pyridinecarbonitrile (BTMSAPyCN)

About 6.17 g of 5-amino-2-pyridinecarbonitrile, 11.54 g oftriethylamine, and 10 ml of toluene were mixed in a round-bottomreaction flask cooled with an ice bath. To this mixture was added, in adropwise fashion, a solution of 25.34 g of trimethylsilyltrifluoromethanesulfonate in 70 ml of toluene. The resulting mixture washeated to reflux for 2.5 hours and then evaporated under vacuum. Theresidue was extracted with 100 ml of hexane. The hexane layer was washedtwice with saturated aqueous sodium bicarbonate solution (80 ml eachtime), dried with anhydrous sodium sulfate, and evaporated under vacuum,yielding 5-[bis(trimethylsilyl)amino]-2-pyridinecarbonitrile (BTMSAPyCN)as a green oil (8.67 g, 64% yield). The ¹H NMR data (C₆D₆, 25° C.,referenced to tetramethylsilane) of the product are listed as follows: δ8.07 (doublet of doubets, 1H, aromatic proton), 6.70 (doublet ofdoublets, 1H, aromatic proton), 6.45 (doublet of doublets, 1H, aromaticproton), −0.16 (singlet, 18H, Si—CH₃ protons). From the ¹H NMR data, thestructure of the product was determined to be as follows:

Example 6 Synthesis of 3-[(Trimethylsilyl)(methyl)amino]propionitrile(3-TMSMAPN)

To a cold solution of 3-(methylamino)propionitrile (23.4 ml) indichloromethane (350 ml) were added triethylamine (38.3 ml) andtrimethylsilyl chloride (33.2 ml). The mixture was stirred at roomtemperature for 18 hours. The triethylamine hydrochloride salt formedwas filtered off and washed with 40 ml of hexane. The combined filtratewas evaporated by using a rotary evaporator. The residual syrup wasdistilled under vacuum to give3-[(trimethylsilyl)(methyl)amino]propionitrile (3-TMSMAPN) as a yellowliquid. The ¹H NMR data (CDCl₃, 25° C., referenced to tetramethylsilane)of the product are listed as follows: δ 3.07 (triplet, 2H, N—CH₂protons), 2.48 (singlet, 3H, N—CH₃ protons), 2.42 (triplet, 2H, CH₂CNprotons), 0.09 (singlet, 9H, Si—CH₃ protons). From the ¹H NMR data, thestructure of the product was determined to be as follows:

Example 7 Synthesis of 3-[(Trimethylsilyl)(ethyl)amino]propionitrile(3-TMSEAPN)

To a cold solution of 3-(ethylamino)propionitrile (10.6 ml) indichloromethane (350 ml) were added triethylamine (14.7 ml) andtrimethylsilyl chloride (12.7 ml). The mixture was stirred at roomtemperature for 18 hours. The triethylamine hydrochloride salt formedwas filtered off and washed with 40 ml of hexane. The combined filtratewas evaporated by using a rotary evaporator. The residual syrup wasdistilled under vacuum to give3-[(trimethylsilyl)(ethyl)amino]propionitrile (3-TMSEAPN) as a yellowliquid. The ¹H NMR data (C₆D₆, 25° C., referenced to tetramethylsilane)of the product are listed as follows: δ 2.54 (triplet, 2H, N—CH₂protons), 2.41 (quartet, 2H, N—CH₂ protons), 1.55 (triplet, 2H, CH₂CNprotons), 0.70 (triplet, 3H, CH₃ protons), 0.00 (singlet, 9H, Si—CH₃protons). From the ¹H NMR data, the structure of the product wasdetermined to be as follows:

Example 8 Synthesis of N-Trimethylsilyl-3,3′-Iminodipropionitrile(TMSIDPN)

To a cold solution of 3,3′-iminodipropionitrile (24.2 ml) indichloromethane (350 ml) were added triethylamine (30.7 ml) andtrimethylsilyl chloride (26.6 ml). The mixture was stirred at roomtemperature for 18 hours. The triethylamine hydrochloride salt formedwas filtered off and washed with 40 ml of hexane. The combined filtratewas evaporated by using a rotary evaporator. The residual syrup wasdistilled under vacuum to giveN-trimethylsilyl-3,3′-iminodipropionitrile (TMSIDPN) as a pale-yellowliquid. The ¹H NMR data (CDCl₃, 25° C., referenced to tetramethylsilane)of the product are listed as follows: δ 3.15 (triplet, 4H, N—CH₂protons), 2.42 (triplet, 4H, N—CH₂ protons), 0.15 (singlet, 9H, Si—CH₃protons). From the ¹H NMR data, the structure of the product wasdetermined to be as follows:

Example 9 Synthesis of Unmodified cis-1,4-Polybutadiene

To a 2-gallon nitrogen-purged reactor equipped with turbine agitatorblades were added 1383 g of hexane and 3083 g of 20.6 wt % 1,3-butadienein hexane. A preformed catalyst was prepared by mixing 7.35 ml of 4.32 Mmethylaluminoxane in toluene, 1.83 g of 20.6 wt % 1,3-butadiene inhexane, 0.59 ml of 0.537 M neodymium versatate in cyclohexane, 6.67 mlof 1.0 M diisobutylaluminum hydride in hexane, and 1.27 ml of 1.0 Mdiethylaluminum chloride in hexane. The catalyst was aged for 15 minutesand charged into the reactor. The reactor jacket temperature was thenset to 65° C. About 60 minutes after addition of the catalyst, thepolymerization mixture was cooled to room temperature and quenched with30 ml of 12 wt % 2,6-di-tert-butyl-4-methylphenol solution inisopropanol. The resulting polymer cement was coagulated with 12 litersof isopropanol containing 5 g of 2,6-di-tert-butyl-4-methylphenol andthen drum-dried. The Mooney viscosity (ML₁₊₄) of the resulting polymerwas determined to be 26.5 at 100° C. by using a Alpha TechnologiesMooney viscometer with a large rotor, a one-minute warm-up time, and afour-minute running time. As determined by gel permeation chromatography(GPC), the polymer had a number average molecular weight (M_(n)) of109,400, a weight average molecular weight (M_(w)) of 221,900, and amolecular weight distribution (M_(w)/M_(n)) of 2.03. The infraredspectroscopic analysis of the polymer indicated a cis-1,4-linkagecontent of 94.4%, a trans-1,4-linkage content of 5.1%, and a 1,2-linkagecontent of 0.5%.

The cold-flow resistance of the polymer was measured by using a Scottplasticity tester. Approximately 2.5 g of the polymer was molded, at100° C. for 20 minutes, into a cylindrical button with a diameter of 15mm and a height of 12 mm. After cooling down to room temperature, thebutton was removed from the mold and placed in a Scott plasticity testerat room temperature. A 5-kg load was applied to the specimen. After 8minutes, the residual gauge (i.e., sample thickness) was measured andtaken as an indication of the cold-flow resistance of the polymer.Generally, a higher residual gauge value indicates better cold-flowresistance.

The properties of the polymer are summarized in Table 1.

TABLE 1 Physical Properties of cis-1,4-Polybutadiene Example No. Example9 Example 10 Example 11 Example 12 Example 13 Example 14 Polymer typeunmodified unmodified 3-BTMSAPN- 4-BTMSAMBZN- 3-BTMSABZN- 4-BTMSABZN-modified modified modified modified ML₁ ₊ ₄ at 100° C. 26.5 44.1 35.528.0 27.6 26.6 Mn 109,400 137,900 116,600 114,500 110,900 110,700 Mw221,900 248,700 239,400 216,800 213,900 212,000 Mw/Mn 2.03 1.80 2.051.89 1.93 1.92 % cis-1,4 94.4 95.0 94.4 94.2 94.2 94.2 % trans-1,4 5.14.5 5.1 5.3 5.3 5.3 % 1,2 0.5 0.5 0.5 0.5 0.5 0.5 Cold-flow gauge 1.652.09 2.34 1.82 1.74 1.76 (mm at 8 min.) Example No. Example 15 Example16 Example 17 Example 18 Example 19 Polymer type BTMSAPyCN- 3-TMSMAPN-3-TMSEAPN- TMSIDPN- DMAMMN- modified modified modified modified modifiedML₁ ₊ ₄ at 100° C. 31.2 35.1 32.9 44.1 31.0 Mn 92,000 112,200 114,800112,000 96,500 Mw 202,000 219,600 216,400 221,200 205,400 Mw/Mn 2.201.96 1.89 1.98 2.13 % cis-1,4 94.2 94.2 94.2 94.2 94.1 % trans-1,4 5.35.3 5.3 5.3 5.4 % 1,2 0.5 0.5 0.5 0.5 0.5 Cold-flow gauge 2.16 2.11 1.982.61 2.01 (mm at 8 min.)

Example 10 Synthesis of Unmodified cis-1,4-Polybutadiene

To a 2-gallon nitrogen-purged reactor equipped with turbine agitatorblades were added 1631 g of hexane and 2835 g of 22.4 wt % 1,3-butadienein hexane. A preformed catalyst was prepared by mixing 6.10 ml of 4.32 Mmethylaluminoxane in toluene, 1.27 g of 22.4 wt % 1,3-butadiene inhexane, 0.49 ml of 0.537 M neodymium versatate in cyclohexane, 5.53 mlof 1.0 M diisobutylaluminum hydride in hexane, and 1.05 ml of 1.0 Mdiethylaluminum chloride in hexane. The catalyst was aged for 15 minutesand charged into the reactor. The reactor jacket temperature was thenset to 65° C. About 72 minutes after addition of the catalyst, thepolymerization mixture was cooled to room temperature and quenched with30 ml of 12 wt % 2,6-di-tert-butyl-4-methylphenol solution inisopropanol. The resulting polymer cement was coagulated with 12 litersof isopropanol containing 5 g of 2,6-di-tert-butyl-4-methylphenol andthen drum-dried. The properties of the resulting polymer are summarizedin Table 1.

Example 11 Synthesis of cis-1,4-Polybutadiene Modified with3-[Bis(trimethylsilyl)amino]propionitrile (3-BTMSAPN)

To a 2-gallon nitrogen-purged reactor equipped with turbine agitatorblades were added 1579 g of hexane and 2886 g of 22.0 wt % 1,3-butadienein hexane. A preformed catalyst was prepared by mixing 7.35 ml of 4.32 Mmethylaluminoxane in toluene, 1.56 g of 22.0 wt % 1,3-butadiene inhexane, 0.59 ml of 0.537 M neodymium versatate in cyclohexane, 6.67 mlof 1.0 M diisobutylaluminum hydride in hexane, and 1.27 ml of 1.0 Mdiethylaluminum chloride in hexane. The catalyst was aged for 15 minutesand charged into the reactor. The reactor jacket temperature was thenset to 65° C. About 60 minutes after addition of the catalyst, thepolymerization mixture was cooled to room temperature.

About 414 g of the resulting unmodified polymer cement (i.e.,pseudo-living polymer cement) was transferred from the reactor to anitrogen-purged bottle, followed by addition of 5.10 ml of 0.500 M3-[bis(trimethylsilyl)amino]propionitrile (3-BTMSAPN) in hexane. Thebottle was tumbled for 30 minutes in a water bath maintained at 65° C.The resulting polymer cement was quenched with 3 ml of 12 wt %2,6-di-tert-butyl-4-methylphenol solution in isopropanol, coagulatedwith 2 liters of isopropanol containing 0.5 g of2,6-di-tert-butyl-4-methylphenol, and then drum-dried. The properties ofthe resulting 3-BTMSAPN-modified polymer are summarized in Table 1.

Example 12 Synthesis of cis-1,4-Polybutadiene Modified with4-[Bis(trimethylsilyl)aminomethyl]benzonitrile (4-BTMSAMBZN)

About 342 g of the pseudo-living polymer cement as synthesized inExample 11 was transferred from the reactor to a nitrogen-purged bottle,followed by addition of 8.07 ml of 0.237 M4-[bis(trimethylsilyl)aminomethyl]benzonitrile (4-BTMSAMBZN) in hexane.The bottle was tumbled for 30 minutes in a water bath maintained at 65°C. The resulting polymer cement was quenched with 3 ml of 12 wt %2,6-di-tert-butyl-4-methylphenol solution in isopropanol, coagulatedwith 2 liters of isopropanol containing 0.5 g of2,6-di-tert-butyl-4-methylphenol, and then drum-dried. The properties ofthe resulting 4-BTMSAMBZN-modified polymer are summarized in Table 1.

Example 13 Synthesis of cis-1,4-Polybutadiene Modified with3-[Bis(trimethylsilyl)amino]benzonitrile (3-BTMSABZN)

About 349 g of the pseudo-living polymer cement as synthesized inExample 11 was transferred from the reactor to a nitrogen-purged bottle,followed by addition of 5.99 ml of 0.326 M3-[bis(trimethylsilyl)amino]benzonitrile (3-BTMSABZN) in hexane. Thebottle was tumbled for 30 minutes in a water bath maintained at 65° C.The resulting polymer cement was quenched with 3 ml of 12 wt %2,6-di-tert-butyl-4-methylphenol solution in isopropanol, coagulatedwith 2 liters of isopropanol containing 0.5 g of2,6-di-tert-butyl-4-methylphenol, and then drum-dried. The properties ofthe resulting 3-BTMSABZN-modified polymer are summarized in Table 1.

Example 14 Synthesis of cis-1,4-Polybutadiene Modified with4-[Bis(trimethylsilyl)amino]benzonitrile (4-BTMSABZN)

About 358 g of the pseudo-living polymer cement as synthesized inExample 11 was transferred from the reactor to a nitrogen-purged bottle,followed by addition of 6.12 ml of 0.328 M4-[bis(trimethylsilyl)amino]benzonitrile (4-BTMSABZN) in hexane. Thebottle was tumbled for 30 minutes in a water bath maintained at 65° C.The resulting polymer cement was quenched with 3 ml of 12 wt %2,6-di-tert-butyl-4-methylphenol solution in isopropanol, coagulatedwith 2 liters of isopropanol containing 0.5 g of2,6-di-tert-butyl-4-methylphenol, and then drum-dried. The properties ofthe resulting 4-BTMSABZN-modified polymer are summarized in Table 1.

Example 15 Synthesis of cis-1,4-Polybutadiene Modified with5-[Bis(trimethylsilyl)amino]-2-pyridinecarbonitrile (BTMSAPyCN)

About 421 g of the pseudo-living polymer cement as synthesized inExample 11 was transferred from the reactor to a nitrogen-purged bottle,followed by addition of 11.3 ml of 0.230 M5-[bis(trimethylsilyl)amino]-2-pyridinecarbonitrile (BTMSAPyCN) intoluene. The bottle was tumbled for 30 minutes in a water bathmaintained at 65° C. The resulting polymer cement was quenched with 3 mlof 12 wt % 2,6-di-tert-butyl-4-methylphenol solution in isopropanol,coagulated with 2 liters of isopropanol containing 0.5 g of2,6-di-tert-butyl-4-methylphenol, and then drum-dried. The properties ofthe resulting BTMSAPyCN-modified polymer are summarized in Table 1.

Example 16 Synthesis of cis-1,4-Polybutadiene Modified with3-[(Trimethylsilyl)(methyl)amino]propionitrile (3-TMSMAPN)

About 343 g of the pseudo-living polymer cement as synthesized inExample 11 was transferred from the reactor to a nitrogen-purged bottle,followed by addition of 5.74 ml of 0.335 M3-[(trimethylsilyl)(methyl)amino]propionitrile (3-TMSMAPN) in toluene.The bottle was tumbled for 30 minutes in a water bath maintained at 65°C. The resulting polymer cement was quenched with 3 ml of 12 wt %2,6-di-tert-butyl-4-methylphenol solution in isopropanol, coagulatedwith 2 liters of isopropanol containing 0.5 g of2,6-di-tert-butyl-4-methylphenol, and then drum-dried. The properties ofthe resulting 3-TMSMAPN-modified polymer are summarized in Table 1.

Example 17 Synthesis of cis-1,4-Polybutadiene Modified with3-[(Trimethylsilyl)(ethyl)amino]propionitrile (3-TMSEAPN)

About 341 g of the pseudo-living polymer cement as synthesized inExample 11 was transferred from the reactor to a nitrogen-purged bottle,followed by addition of 5.11 ml of 0.373 M3-[(trimethylsilyl)(ethyl)amino]propionitrile (3-TMSEAPN) in hexane. Thebottle was tumbled for 30 minutes in a water bath maintained at 65° C.The resulting polymer cement was quenched with 3 ml of 12 wt %2,6-di-tert-butyl-4-methylphenol solution in isopropanol, coagulatedwith 2 liters of isopropanol containing 0.5 g of2,6-di-tert-butyl-4-methylphenol, and then drum-dried. The properties ofthe resulting 3-TMSEAPN-modified polymer are summarized in Table 1.

Example 18 Synthesis of cis-1,4-Polybutadiene Modified withN-Trimethylsilyl-3,3′-Iminodipropionitrile (TMSIDPN)

About 371 g of the pseudo-living polymer cement as synthesized inExample 11 was transferred from the reactor to a nitrogen-purged bottle,followed by addition of 5.75 ml of 0.361 MN-trimethylsilyl-3,3′-iminodipropionitrile (TMSIDPN) in toluene. Thebottle was tumbled for 30 minutes in a water bath maintained at 65° C.The resulting polymer cement was quenched with 3 ml of 12 wt %2,6-di-tert-butyl-4-methylphenol solution in isopropanol, coagulatedwith 2 liters of isopropanol containing 0.5 g of2,6-di-tert-butyl-4-methylphenol, and then drum-dried. The properties ofthe resulting TMSIDPN-modified polymer are summarized in Table 1.

Example 19 Synthesis of cis-1,4-Polybutadiene Modified with(Dimethylaminomethylene)malononitrile (DMAMMN)

To a 2-gallon nitrogen-purged reactor equipped with turbine agitatorblades were added 1526 g of hexane and 2940 g of 21.6 wt % 1,3-butadienein hexane. A preformed catalyst was prepared by mixing 8.82 ml of 4.32 Mmethylaluminoxane in toluene, 1.91 g of 21.6 wt % 1,3-butadiene inhexane, 0.71 ml of 0.537 M neodymium versatate in cyclohexane, 8.00 mlof 1.0 M diisobutylaluminum hydride in hexane, and 1.52 ml of 1.0 Mdiethylaluminum chloride in hexane. The catalyst was aged for 15 minutesand charged into the reactor. The reactor jacket temperature was thenset to 65° C. About 50 minutes after addition of the catalyst, thepolymerization mixture was cooled to room temperature.

About 355 g of the resulting unmodified polymer cement (i.e.,pseudo-living polymer cement) was transferred from the reactor to anitrogen-purged bottle, followed by addition of 14.1 ml of 0.169 M(dimethylaminomethylene)malononitrile (DMAMMN) in toluene. The bottlewas tumbled for 30 minutes in a water bath maintained at 65° C. Theresulting polymer cement was quenched with 3 ml of 12 wt %2,6-di-tert-butyl-4-methylphenol solution in isopropanol, coagulatedwith 2 liters of isopropanol containing 0.5 g of2,6-di-tert-butyl-4-methylphenol, and then drum-dried. The properties ofthe resulting DMAMMN-modified polymer are summarized in Table 1.

Examples 20-27 Compounding Evaluation of 3-BTMSAPN-, 4-BTMSAMBZN-,3-BTMSABZN-, 4-BTMSABZN-, BTMSAPyCN-, 3-TMSMAPN-, 3-TMSEAPN-, TMSIDPN-,and DMAMMN-Modified cis-1,4-Polybutadiene vs. Unmodifiedcis-1,4-Polybutadiene

The cis-1,4-polybutadiene samples produced in Examples 9-19 wereevaluated in a rubber compound filled with carbon black. Thecompositions of the vulcanizates are presented in Table 2, wherein thenumbers are expressed as parts by weight per hundred parts by weight oftotal rubber (phr).

TABLE 2 Compositions of Rubber Vulcanizates Prepared fromcis-1,4-Polybutadiene Ingredient Amount (phr) cis-1,4-Polybutadiene 80sample Polyisoprene 20 Carbon black 50 Oil 10 Wax 2 Antioxidant 1 Zincoxide 2.5 Stearic acid 2 Accelerators 1.3 Sulfur 1.5 Total 170.3

The Mooney viscosity (ML₁₊₄) of the uncured rubber compound wasdetermined at 130° C. by using a Alpha Technologies Mooney viscometerwith a large rotor, a one-minute warm-up time, and a four-minute runningtime. The hysteresis data (tans) and the Payne effect data (ΔG′) of thevulcanizates were obtained from a dynamic strain-sweep experiment, whichwas conducted at 50° C. and 15 Hz with strain sweeping from 0.1% to 20%.ΔG′ is the difference between G′ at 0.1% strain and G′ at 20% strain.The physical properties of the vulcanizates are summarized in Table 3.In FIG. 2, the tan δ data are plotted against the compound Mooneyviscosities.

TABLE 3 Physical Properties of Rubber Vulcanizates Prepared fromcis-1,4-Polybutadiene Example No. Example 20 Example 21 Example 22Example 23 Example 24 Example 25 Polymer used Example 9 Example 10Example 11 Example 12 Example 13 Example 14 Polymer type unmodifiedunmodified 3- 4- 3- 4- BTMSAPN- BTMSAMBZN- BTMSABZN- BTMSABZN- modifiedmodified modified modified Compound ML₁ ₊ ₄ 49.7 64.6 65.2 66.6 60.560.6 at 130° C. tanδ at 50° C., 3% 0.155 0.139 0.116 0.0975 0.105 0.111strain ΔG′ (MPa) 3.16 2.74 2.57 1.46 1.65 2.18 Example No. Example 26Example 27 Example 28 Example 29 Example 30 Polymer used Example 15Example 16 Example 17 Example 18 Example 19 Polymer type BTMSAPyCN- 3-3- TMSIDPN- DMAMMN- modified TMSMAPN- TMSEAPN- modified modifiedmodified modified Compound ML₁ ₊ ₄ 70.4 58.7 56.9 61.7 51.6 at 130° C.tanδ at 50° C., 3% 0.0972 0.130 0.129 0.120 0.121 strain ΔG′ (MPa) 1.512.73 2.61 2.42 2.52

As can be seen in Table 3 and FIG. 2, the 3-BTMSAPN-, 4-BTMSAMBZN-,3-BTMSABZN-, 4-BTMSABZN-, BTMSAPyCN-, 3-TMSMAPN-, 3-TMSEAPN-, TMSIDPN-,and DMAMMN-modified cis-1,4-polybutadiene samples give lower tans thanthe unmodified polymer, indicating that the modification ofcis-1,4-polybutadiene with 3-BTMSAPN, 4-BTMSAMBZN, 3-BTMSABZN,4-BTMSABZN, BTMSAPyCN, 3-TMSMAPN, 3-TMSEAPN, TMSIDPN, and DMAMMN reduceshysteresis. The modified cis-1,4-polybutadiene samples also give lowerΔG′ than the unmodified polymer, indicating that the Payne Effect hasbeen reduced due to the stronger interaction between the modifiedpolymer and carbon black.

Various modifications and alterations that do not depart from the scopeand spirit of this invention will become apparent to those skilled inthe art. This invention is not to be duly limited to the illustrativeembodiments set forth herein.

1. A method for preparing a functionalized polymer, the methodcomprising the steps of: (i) polymerizing monomer with a coordinationcatalyst to form a reactive polymer; and (ii) reacting the reactivepolymer with a nitrile compound containing a protected amino group. 2.The method of claim 1, where the protected amino group is selected fromthe group consisting of bis(trihydrocarbylsilyl)amino,bis(dihydrocarbylhydrosilyl)amino, 1-aza-disila-1-cyclohydrocarbyl,(trihydrocarbylsilyl)(hydrocarbyl)amino,(dihydrocarbylhydrosilyl)(hydrocarbyl)amino,1-aza-2-sila-1-cyclohydrocarbyl, dihydrocarbylamino, and1-aza-1-cyclohydrocarbyl groups.
 3. The method of claim 1, where thenitrile compound containing a protected amino group is defined by theformula I:

where R¹ is a divalent organic group, and R² and R³ are eachindependently a mono-valent organic group or a hydrolyzable group, or R²and R³ join to form a divalent organic group.
 4. The method of claim 3,where the nitrile compound containing a protected amino group is definedby the formula II

where R¹ and R⁵ are each independently a divalent organic group, and R⁴and R⁶ are each independently a bond or a hydrolyzable group.
 5. Themethod of claim 3, where the nitrile compound containing a protectedamino group is defined by the formula III:

where R¹ is a divalent organic group, and R⁷ and R⁸ are eachindependently a hydrogen atom or a mono-valent organic group, or atleast one R⁷ and at least one R⁸ join to form a divalent organic group.6. The method of claim 5, where the nitrile compound containing aprotected amino group is defined by the formula IV:

where R¹ and R⁵ are each independently a divalent organic group, and R⁷and R⁸ are each independently a hydrogen atom or a mono-valent organicgroup.
 7. The method of claim 1, where the nitrile compound containing aprotected amino group derives from a nitrile compound selected from thegroup consisting of arenecarbonitrile compounds, alkanecarbonitrilecompounds, alkenecarbonitrile compounds, alkynecarbonitrile compounds,cycloalkanecarbonitrile compounds, cycloalkenecarbonitrile compounds,cycloalkynecarbonitrile compounds, and heterocyclic nitrile compounds.8. The method of claim 1, where the monomer is conjugated diene monomer.9. The method of claim 1, where said step of reacting produces areaction product that is subsequently protonated.
 10. The method ofclaim 1, where the coordination catalyst is a lanthanide-based catalyst.11. The method of claim 10, where the lanthanide-based catalyst includes(a) a lanthanide-containing compound, (b) an alkylating agent, and (c) ahalogen source.
 12. The method of claim 11, where the alkylating agentincludes an aluminoxane and an organoaluminum compound represented bythe formula AlR_(n)X_(3-n), where each R, which may be the same ordifferent, is a monovalent organic group that is attached to thealuminum atom via a carbon atom, where each X, which may be the same ordifferent, is a hydrogen atom, a halogen atom, a carboxylate group, analkoxide group, or an aryloxide group, and where n is an integer of 1 to3.
 13. The method of claim 1, where said step of polymerizing monomertakes place within a polymerization mixture including less than 20% byweight of organic solvent.
 14. A functionalized polymer defined by theformula:

where π is a cis-1,4-polydiene chain having a cis-1,4-linkage contentthat is greater than 60%, R¹ is a divalent organic group, and R² and R³are each independently a mono-valent organic group or a hydrolyzablegroup, or R² and R³ join to form a divalent organic group.
 15. Thefunctionalized of claim 14, where π is a cis-1,4-polydiene chain havinga cis-1,4-linkage content that is greater than 90%.
 16. A functionalizedpolymer defined by the formula:

where π is a cis-1,4-polydiene chain having a cis-1,4-linkage contentthat is greater than 60%, R¹ is a divalent organic group, and R² and R³are each independently a mono-valent organic or a hydrogen atom, or R²and R³ join to form a divalent organic group.
 17. The functionalized ofclaim 16, where π is a cis-1,4-polydiene chain having a cis-1,4-linkagecontent that is greater than 90%.
 18. A tire component comprising thepolymer of claim
 17. 19. A functionalized polymer prepared by the stepsof: (i) polymerizing conjugated diene monomer with a coordinationcatalyst to form a reactive cis-1,4-polydiene having a cis-1,4-linkagecontent that is greater than 60%; and (ii) reacting the reactivecis-1,4-polydiene with a nitrile compound containing a protected aminogroup.
 20. A tire component prepared by employing the functionalizedpolymer of claim
 19. 21. A vulcanizable composition comprising: thefunctionalized polymer of claim 19, a filler, and a curative.